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acid, which can be generated from biomass raw materials through fermentation. In this work, an
overview regarding the main properties and applications of ethyl lactate, as well as its synthesis and
production processes, with a particular emphasis on reactive/separation processes, is presented.
1. Introduction
Organic esters are a very important class of chemicals having
applications in a variety of areas in the chemical industry, such
as perfumes, flavours, pharmaceuticals, plasticizers, solvents and
intermediates.1 Ethyl lactate is an important monobasic ester,
also known as lactic acid ethyl ester (IUPAC name: Ethyl (S)-
2-hydroxypropanoate), with molecular formula C5 H10 O3 (see
Fig. 1). It is a clear to slightly yellow liquid, and it is found
naturally in small quantities in a wide variety of foods, including
wine, chicken, and some fruits.
Ethyl lactate can be either in the levo (S) or dextro (R) forms,
and it is industrially produced as a racemic mixture through
a reversible reaction between ethanol and lactic acid, wherein
water is a by-product. Lactic acid itself is a very important
chemical with applications in the food, pharmaceutical and
Fig. 1 The molecular structure of ethyl lactate.
cosmetic industries. It is also used as a monomer for the manu-
facture of biodegradable polymers, as substitutes for traditional
tion and environmental regulation were mainly nation based,
petrochemical polymers. Lactic acid has been produced through
until the 1980s. Since then, with the increase of international
both chemical synthesis or fermentation routes. This last pro-
chemical trade and the knowledge of the impact of global
cess is the most common,2 however, lactic acid derived from
trade on the environment, international environmental treaties,
fermentation broths requires extensive purification processes
directives, and conventions have emerged.5 Moreover, it was in
that should be inexpensive and environmentally friendly. Ethyl
the 1980s that environmental protection was connected with
lactate hydrolysis is one of the methods used to obtain pure lactic
economic development, leading to dissemination of “sustainable
acid.3,4
development” as a means to encourage the integration of
Ethyl lactate has attracted much attention in recent years,
policies across sectors (Rio Declaration on Environment and
which is reflected in the number of articles published, as shown
Development and Johannesburg Declaration on Sustainable
in Fig. 2. This is probably due to the environmental movement
Development, informally known as Earth Summit 1992 and
that emerged in the 1970s (United Nations Conference on the
2002, respectively). Furthermore, with the Yom Kippur War
Human Environment at Stockholm in 1972). Chemical legisla-
(1973) and the subsequent Arab Oil Embargo, the Iranian
Revolution (between November 1978 and June 1979), and
Laboratory of Separation and Reaction Engineering (LSRE), Associate the Iraq–Iran War (1980), crude oil production declined, and,
Laboratory LSRE/LCM, Department of Chemical Engineering, Faculty consequently, the crude oil price increased drastically, from 3
of Engineering, University of Porto, Rua Dr Roberto Frias s/n, USD per barrel in 1972 up to 35 USD in 1981. More recently,
4200-465, Porto, Portugal. E-mail: viviana.silva@fe.up.pt; Fax: +351
225081674; Tel: +351 225081489 the PDVSA strike (Venezuela, 2002–2003) and the Iraq War
2658 | Green Chem., 2011, 13, 2658–2671 This journal is © The Royal Society of Chemistry 2011
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Carla Pereira was born in 1980 in Coimbra, Portugal. She obtained her Ph.D. degree in Chemical and Biological Engineering from
Porto University (FEUP) in 2009 working on process intensification for the sustainable production of ethyl lactate based on membrane
and chromatographic reactors under the supervision of Professor Alı́rio Rodrigues and Dr Viviana Silva. This work was developed in
the Laboratory of Separation and Reaction Engineering, where she is currently working as a post-doctoral fellow. Her research interests
focus on integrated reaction and separation processes, particularly, simulated moving bed reactor and pervaporation membrane reactors,
for diesel additives and green solvents production.
Viviana Silva (1974) received her Ph.D. in Chemical Engineering from University of Porto (Portugal) in 2003. In 2001, she was Assistant
Professor at Instituto Politécnico de Bragança (Portugal) and, in 2006, she joined Fluidinova (Portugal) as Group Leader. In November
2007, she returned to the Associated Laboratory LSRE/LCM (University of Porto) as Assistant Researcher. Her primary interest is the
process intensification of green fuels and solvents, being awarded with the 1st prize “IChemE Awards for Innovation & Excellence 2008”,
in the category “ABB Global Consulting Award for Sustainable Technology”. Since 2006, she is also developing continuous processes for
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G
Alı́rio E. Rodrigues is Professor of Chemical Engineering at the University of Porto (Portugal). He graduated in Chemical Engineering
from the University of Porto in 1968 and received his Dr-Ing degree at the University of Nancy (France) in 1973. He is Director of
the Associate Laboratory LSRE/LCM (http://lsre.fe.up.pt). His main research interests are in cyclic separation/reaction processes
(simulated moving bed, pressure swing adsorption, and parametric pumping), chemical reaction engineering and product engineering
(perfume engineering and microencapsulation).
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the crude oil price reached a new maximum of 126 USD per
barrel in June 2008, followed by a drastic drop due to the
financial crisis, being currently at about 94 USD.6 Considering
both the environmental regulations, as well as the increase in
crude oil prices, the search for greener chemicals obtained from
renewable sources is imperative for sustainable development.
The most popular green solvents are water (aqueous biphasic),
supercritical carbon dioxide and ionic liquids.7 In spite of the
increasing interest, less attention is being given to bio-based
solvents, such as the lactate ester family solvents,8 in which ethyl
lactate is the most important member.
Currently, a great challenge is the design and implementa-
tion of completely green products and processes. There is no
systematic and reliable method to ensure that the chemistry
Fig. 2 Publications related to ethyl lactate since 1980 using all implemented is green, since the number of chemical synthesis
databases. Total number of publications with “ethyl lactate” in the pathways is vast, and in general it is only possible to verify
topic = 1566. Total number of publications with “ethyl lactate” in if a proposed manufacturing process is “greener” than other
the title = 304. Total number of publications with “ethyl lactate” + alternatives. Anastas and Warner have developed the “Twelve
“synthesis” = 51. Data were obtained from ISI Web of Knowledge on Principles of Green Chemistry”, which are a list of suggestions
5th of July 2011. on how to design a greener process and/or a greener product,9
which are:
(2003), together with a weak dollar and the continued rapid 1. It is better to prevent waste than to treat or clean up waste
growth in Asian economies and their petroleum consumption, after it is formed.
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2. Synthetic methods should be designed to maximize the avoids the use of corrosive catalysts and, thus, eliminates a
incorporation of all materials used in the process into the final further step of their neutralization: 1st and 9th principles.
product. 4) Ethyl lactate can be produced by using hybrid technologies
3. Wherever practicable, synthetic methodologies should be where reaction and separation of at least one product take place
designed to use and generate substances that possess little or no in a single unity eliminating the use of solvents, reducing the
toxicity to human health and the environment. capital cost (less separation units are needed) and requiring less
4. Chemical products should be designed to preserve efficacy energy consumption: 5th and 6th principles.
of function while reducing toxicity. In summary, as shown in Fig. 3, ethyl lactate can be easily
5. The use of auxiliary substances (e.g. solvents, separation obtained by carbohydrate feedstocks, since it is produced from
agents, etc.) should be made unnecessary whenever possible and, ethanol and lactic acid that are obtained by fermentation of
innocuous when used. biomass, as corn starch crops; and it is a biodegradable com-
6. Energy requirements should be recognized for their en- pound with good properties to be applied as a green solvent in
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G
vironmental and economic impacts and should be minimized. several applications, such as organic synthesis, pharmaceutical
Synthetic methods should be conducted at ambient temperature preparations, fragrances, for inks and coatings industries, and
and pressure. food additives.
7. A raw material or feedstock should be renewable rather than
depleting whenever technically and economically practical.
8. Unnecessary derivatization (blocking group, protec-
tion/deprotection, and temporary modification of physi-
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Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G
Ethanol platform
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increase of crude oil prices and with the further technological green solvent more commercially attractive, and due to the rising
development of lactic acid production, it is expected that this environmental consciousness, some consumers are willing to pay
compound will become cheap enough in order to offer a more for products that are less detrimental to the environment.
biomass-based route to produce propylene glycol. Weis and Visco,41 developed a study using computer-aided
molecular design to identify potential new environmentally
friendly solvents as a supplement to GlaxoSmithKline’s solvent
selection guide,42 and ethyl lactate was presented as one of the
potential solvents. This evidence is supported by many references
documenting ethyl lactate applications as an environmentally
friendly solvent, presented below.
Ethyl lactate is a desirable coating for wood, polystyrene and
metals and also acts as a very effective paint stripper and graffiti
remover. It can also be used in magnetic tape coatings replacing
the hazardous air pollutants (MEK, MIBK and toluene).43
Ethyl lactate is replacing solvents, such as N-methyl pyrrolidone
(NMP),44 toluene, acetone and xylene, which has resulted in a
safer workplace. In Table 1, the solvating properties of ethyl
lactate and NMP are presented.
Fig. 6 Some potential derivatives of lactic acid.28,35
Other applications of ethyl lactate are as a cleaning agent
for the polyurethane industry and for metal surfaces, efficiently
Ethyl lactate properties and applications removing greases, oils, adhesives and solid fuels. Recently, it
also been shown to be effective on the removal of copper from
Ethyl lactate can be used as a food additive, in perfumery, contaminated soils.45 Ethyl lactate can also be applied in the
as flavour chemicals and solvent, which can dissolve acetic pharmaceutical industry as a dissolving/dispersing excipient for
acid cellulose and many resins.37 Its main application is as a various biologically active compounds without destroying the
solvent, being particularly attractive for the coatings industry pharmacological activity of the active ingredient. It is a very
as a result of its high solvency power, high boiling point, low effective agent for solubilising biologically active compounds
vapour pressure and low surface tension. Some physical and that are difficult to solubilise in usual excipients.46,47 Ethyl lactate
thermodynamic properties of ethyl lactate as well of the species can also be used as a more environmentally friendly alternative
involved in its synthesis are presented in the Appendix.
Almost all manufacturing and processing industries depend
Table 1 The solvating properties of ethyl lactate and N-methyl
on the use of solvents (see Fig. 7). Some industry experts suggest pyrrolidone
that ethyl lactate could replace the traditional solvents in more
than 80% of their applications.38 However, this is probably N-Methyl
Ethyl lactate pyrrolidone
highly inflated, since ethyl lactate is a high boiling polar protic
Kauri Butanol(KB) Value >1000 350
solvent13 and there are applications where non-polar, aprotic
and/or lower boiling point solvents are required. Annually, just Solubility Hildebrand parameter 21.3 23.1
in the U.S.A, the solvents demand is about 10 billion pounds parameters
Disperse Hansen parameter 7.8 8.8
at prices from $0.90 to $1.70 per pound. Selling prices for
Polar Hansen parameter 3.7 6.0
ethyl lactate have ranged from $1.50 to $2.00 per pound, but
2662 | Green Chem., 2011, 13, 2658–2671 This journal is © The Royal Society of Chemistry 2011
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Table 2 The major advantages of ethyl lactate The self-esterification degree increases with increasing acid
concentration. This makes the use of lactic acid difficult as
Ethyl Lactate Benefits
a reactant for ethyl lactate synthesis, since the use of a high
100% Biodegradable Renewable – made from corn and lactic acid concentration implies the presence of lactic acid
other carbohydrates oligomers during the esterification, which will be converted into
FDA approved as a flavour EPA approved SNAP solvent the corresponding esters that simultaneously undergo hydrolysis
additive
Non carcinogenic Non corrosive
and transesterification, leading to a mixture of acid and ester
Great penetration Stable in solvent formulations until monomer and oligomers:
characteristics exposed to water
Rinses easily with water High solvency power for resins, 2La1 ¤ La2 + W (lactic acid dimer formation)
polymers and dyes
High boiling point Easy and inexpensive to recycle
Low VOC Not an ozone depleting chemical
La1 + La2 ¤ La3 + W (lactic acid trimer formation)
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G
The use of lactic acid and ethanol as reactants for the ethyl
lactate synthesis has the advantage of both being produced
from renewable resources (by glucose or sugar fermentation
processes).
Lactic acid has a bifunctional nature (contains a hydroxyl
group adjacent to the carboxylic acid) and thus it undergoes
intermolecular esterification in aqueous solutions above 20 wt%
to form a linear dimer, and higher oligomer acids.55,56 An 88 Some of the kinetic studies regarding ethyl lactate syn-
wt% lactic acid solution comprises 43.5 mol% of monomer thesis are performed using a 20 wt% lactic acid solution in
(La1 ), 9.2 mol% of dimer (La2 ), 1.8 mol% of trimer (La3 ) and order to avoid the formation of oligomers, but even when
about 45 mol% of water. On the other hand a 20 wt% aqueous higher lactic acid concentrations are used, the presence of
solution of lactic acid is constituted only by monomer and oligomers is normally neglected. Just two works take into
water, with a monomer molar percentage of about 5.6 mol%.57 account the oligomers; however, their amount is less than 5%
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Table 3 Summary of the kinetic studies of the esterification reaction between ethanol and lactic acid
Troupe and DiMilla, 195761 Sulfuric acid 25–100 ◦ C 85; 44 neglected empirical equation concentrations 62.47
Tanaka et al., 200237 Amberlyst 15 90–92 ◦ C 91 considered simple nth-order concentrations 47.00c
reversible rate
expressions
Benedict et al., 200362 Without catalyst 95 ◦ C 88 neglected homogeneous concentrations —
Amberlyst XN-1010 75–95 ◦ C 88 neglected based on single-site concentrations 30.54
mechanisms
Engin et al., 200363 Heteropoly acid 70 ◦ C 92 neglected simple nth-order concentrations —
supported on reversible rate
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G
Lewatit
R S100 expressions
Zhang et al., 200464 002 60–88 ◦ C 20 neglected Langmuir– activitiesa 51.58
Hinshelwood
NKC Langmuir– activitiesa 52.26
Hinshelwood
57 ◦
Asthana et al., 2006 Amberlyst 15 62–90 C 20; 50; 88 considered simple nth-order concentrations 48.00c
reversible rate
expressions
Delgado et al., 200760 Amberlyst 15 55–86 ◦ C 20 neglected Langmuir– activitiesb 52.29
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Hinshelwood
◦
Without catalyst 55–85 C 20 neglected homogeneous activitiesb 62.50
Pereira et al., 200858 Amberlyst 15 50–90 ◦ C 88 neglected Langmuir– activitiesb 49.98
Hinshelwood
Bamoharram et al., 201065 Preyssler acid 70–85 ◦ C 20 neglected simple nth-order concentrations 47.11
reversible rate
expressions
a
activity coefficients calculated by the UNIFAC model. b activity coefficients calculated by the UNIQUAC model. c activation energy of the lactic
acid monomer esterification.
at equilibrium.37,57 The extent of oligomer formation depends equilibrium constant defined as function of the species liquid
on the water concentration, but also on the ethanol contents; activities, described by the following expression: ln(K) = 2.9625
for example, for a lactic acid solution of 88 w.%, the oligomers - 515.13/T(K).58 There is another work regarding the vapour–
composition at equilibrium is 2.4 molar% when using a molar liquid reactive equilibrium for the ethyl lactate synthesis,59 where
ratio between ethanol and lactic acid of 1 and of 0.4 molar% the thermodynamic equilibrium constant is also determined,
when using an ethanol : lactic acid molar ratio of 3.58 but the values predicted by the proposed equilibrium constant
Esterifications are self-catalyzed reactions, since the H+ cation expression present high deviations from the experimental ones.
released from the partial dissociation of the carboxylic acid As mentioned previously, the hydrolysis of ethyl lactate is also
used as a reactant catalyses the reaction. However, the use of an important reaction since it can be used to obtain highly pure
a catalyst is favourable for the reaction rate as the kinetics of the lactic acid. However, just one work presents a study regarding
self-catalyzed reaction are extremely slow, since its rate depends this subject.60
on the autoprotolysis of the carboxylic acid. For example, the
lactic acid acidity constant is pK a = 3.86 at 25 ◦ C, and therefore
5. Production processes
an aqueous solution with 85% of lactic acid (about 10.8 M)
has a pH = 1.4. Typically, the catalytic production of lactates There are a considerable number of patented processes for ethyl
is performed with homogeneous catalysts using acids, such lactate production; in most of them, the esterification reaction
as sulphuric acid, phosphoric acid and anhydrous hydrogen between ethanol and lactic acid is carried out until equilibrium
chloride. However, the use of a heterogeneous catalyst (as for and then the ethyl lactate is separated from the reaction mixture
example, zeolites, ion-echange resins like Amberlyst 15-wet, by distillation. In order to overcome the equilibrium limitation,
Nafion NR50, among others) has clear advantages, i.e.: easy an excess of ethanol is applied and a strong acid is used as
to separate from the reaction mixture; long life time; higher a catalyst, the most common being sulphuric acid.66–69 There
purity of products (side reactions can be eliminated or are are similar processes, but using ammonium lactate instead of
less significant); and elimination of the corrosive environment lactic acid.70–75 A recent work76 presents the synthesis of ethyl
caused by the discharge of acid containing waste. A summary lactate from ammonium lactate solution by the coupling of
of the kinetic studies performed for lactic acid esterification solvent extraction with esterification. Dimethyl sulfoxide, N-
with ethanol is presented in Table 3. As can be seen, the kinetic methyl pyrrolidine and triethyl phosphate were evaluated as
model is usually expressed in terms of species concentration; solvents, but the last proved to be the most efficient.
few authors take into account the non-ideality of the reaction Arkema (France) has two patented processes related to
mixture using activities instead of concentration. There are a continuous ethyl lactate production from the esterification
reasonable number of kinetic studies for this system available reaction between lactic acid and ethanol using sulphuric acid
in the literature; however, only one presents the thermodynamic as catalyst. One consists of extracting a mixture comprising
2664 | Green Chem., 2011, 13, 2658–2671 This journal is © The Royal Society of Chemistry 2011
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ethyl lactate, ethanol, water and different heavy products from this is followed by separation of the reaction mixture in two
the reaction medium at partial lactic acid conversion rate consecutive distillation columns or, alternatively, by several
and, then, feeding the mixture to a reduced-pressure flash pervaporation steps (see Fig. 8).81 It is reported that a lactic
separation, producing an overhead stream containing a mixture acid conversion of 99% and an ethyl lactate purity of 76% was
of ethyl lactate, ethanol and water, that is subjected to a obtained, for an initial ethanol/lactic acid molar ratio of 2 : 1, a
fractional distillation column.77,78 The other is characterized by reaction mixture temperature of 95 ◦ C, a permeate-side vacuum
the continuous extraction of a near-azeotropic water/ethanol pressure less than 0.5 mbar and, as the catalyst, an ion-exchange
gas mixture from the reaction medium, followed by dehydration resin, Amberlyst XN-1010, at 10% of lactic acid weight.
of this mixture using molecular sieves, where two streams are
obtained: an ethanol gas stream that is recycled to the reaction
medium; and a water/ethanol stream that is fed to a distillation
column.79,80 An ethyl lactate purity higher than 95% is reported in
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G
Rathin and GFT PerVap 1005 95 ◦ C 1.20 Amberlyst XN-1010 2.0 99% 76%
Shih-Perng,
199881
Jafar et al., 200286 zeolite A 70 ◦ C 0.18 p-toluene sulphonic acid 2.0 95% —
Tanaka et al., zeolite T 120 ◦ C 0.33 Amberlyst 15 2.4 99% —
200237
Benedict et al. GFT PerVap 1005 95 ◦ C — Amberlyst XN-1010 1.2 71%d —
2003, 200662,82
Budd, et al., zeolite/polyelectrolyte 100 ◦ C 0.60b p-toluenesulfonic acid 2.0 90% —
200487 multilayer
c
0.19
Ma et al., 200984 chitosan–TEOS 80 ◦ C 0.27 Amberlyst 15 3.0 80%e —
Pereira et al., Microporous silica 70 ◦ C 2.55 Amberlyst 15 1 98% 96%
201088
a
for water/ethanol liquid mixture (ª10/90 wt%); b sheet membrane (70 ◦ C); c tube membrane (70 ◦ C); d after 8 h; e after 9 h.
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Fig. 9 The layout of a pervaporation membrane reactor: (i) batch reactor with an external pervaporation unit; (ii) membrane and reactor in the
same unit; (iii) continuous integrated membrane reactor.
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Table 5 Basic properties of lactic acid, ethanol, ethyl lactate and water95
additional separation steps. In order to achieve high ethyl lactate lactate productivity, but with the penalty of the consumption
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G
productivity without the penalty on the consumption of ethanol, of desorbent, which should be further separated and recycled
a new technology was recently developed: the simulated moving in the SMBR unit, two subsequent separation units being
bed membrane reactor (PermSMBR), which comprises the necessary. PermSMBR seems the most promising technology
integration of hydrophilic membranes into the SMBR columns93 for ethyl lactate production, since it operates at moderate
(Fig. 13). These membranes enhance the water removal, allowing temperatures (70 ◦ C), and results in high ethyl lactate production
the elimination of the extract stream and leading to a better rates, low desorbent consumption and just one additional
performance for ethyl lactate production, as shown in the work separation step to separate ethyl lactate from ethanol. However,
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of Silva and collaborators.94 For ethyl lactate synthesis, the RD it requires vacuum costs and the limitations associated with the
and SMBR processes require more than 152% and 165% of membranes’ stability/durability are also an issue. Moreover, the
the ethanol consumption, respectively, of the new PermSMBR proof-of-concept of this technology has not yet been performed.
technology. A fair comparison of technologies must be done in terms of
economic and environmental impact assessment, in order to
determine the most viable process for the efficient production of
ethyl lactate.
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Table 6 Constants used for density calculation95 Table 9 Ethyl lactate viscosity for different temperatures at atmo-
spheric pressure
Constants Lactic Acid Ethanol Water Ethyl Lactate
h (cP) 278.15 K 298.15 K 318.15 K
A 0.39816 0.26570 0.34710 0.33372
B 0.26350 0.26395 0.27400 0.21190 Estimated by Eq. A.7 (Ref. 95) 4.55 2.21 1.26
n 0.28570 0.23670 0.28571 0.45530 Experimental (Ref. 97) — 2.40 —
T min (K) 291.15 159.05 273.16 247.15 Experimental (Ref. 98,99) 4.75 2.53 1.6
T max (K) Tc Tc Tc Tc
Reference Temperature
TR (K) Lactic Acid Ethanol Ethyl Lactate Water
Table 11 Constants used for vapour pressure calculation95
293.15 74.640 58.174 113.986 18.082
Constants Lactic Acid Ethanol Water Ethyl Lactate
V R is the molar volume at the reference temperature T R A -27.0836 23.8442 29.8605 32.0863
B -3.9661 ¥ 103 -2.8642 ¥ 103 -3.1522 ¥ 103 -2.9164 ¥ 103
(cm3 mol-1 ), w is the acentric factor and T c is the critical T/K.
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Viscosity
Table 12 Constants used for heat capacity calculation95
The correlation for liquid viscosity as a function of temperature
Constants Ethanola Watera Ethyl Lactate Lactic acida
is given by eqn (A.7) (see constants in Table 8).
A 1.0264 ¥ 105 2.7637 ¥ 105 -46.239 6.1082 ¥ 104
B
log10 hL = A + + CT + DT 2 (A.7) B -1.3963 ¥ 102 -2.0901 ¥ 103 2.1823 5.0343 ¥ 102
T C -3.0341 ¥ 10-2 8.1250 -5.9832 ¥ 10-3 —
D 2.0386 ¥ 10-3 -1.4116 ¥ 10-2 6.8683 ¥ 10-6 —
with hL (cP) and T/K. E — 9.3701 ¥ 10-6 — —
Ethyl lactate viscosity data are very scarce in the literature. T min (K) 159.05 273.16 248.00 289.90
T max (K) 390.00 533.15 529.00 675.00
Some works just present the viscosity of this compound at a Error <3% <1% — <10%
single temperature.97 However, in the works of Aparicio and
a
Alcalde the values of ethyl lactate viscosity for a wide range parameters taken from ref. 100.
of pressures and temperatures are reported.98,99 In Table 9,
the viscosities of ethyl lactate estimated by the correlation
mentioned above (eqn (A.7)) and experimentally measured are Table 13 Constants used for heat vaporization calculation100
presented. As can be seen, the correlation estimates smaller
Constants Ethanol Water Ethyl Lactate Lactic acid
viscosity values than the ones obtained experimentally. At
278.15 K, the correlation leads to a value 4% smaller than the A 5.5789 ¥ 107 5.2053 ¥ 107 8.0260E ¥ 107 1.0436 ¥ 108
value reported in Aparicio and Alcalde.98,99 B 3.1245 ¥ 10-1 3.1990 ¥ 10-1 4.0930 ¥ 10-1 3.8548 ¥ 10-1
The lactic acid viscosity might be estimated by the following C — -2.1200 ¥ 10-1 — —
D — 2.5795 ¥ 10-1 — —
expression:100 T min (K) 159.05 273.16 247.15 289.90
T max (K) 514.00 647.13 588.00 675.00
⎛ 4097.9 ⎞
hLA = exp ⎜⎜−14.403 + − 0.4407 × ln(T )⎟⎟⎟ (A.8) Error <1% <1% <10% <25%
⎜⎝ T ⎠
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with Pvp (mmHg) and T/K.95 The constants used in the vapour
Published on 15 August 2011 on http://pubs.rsc.org | doi:10.1039/C1GC15523G
Fig. 14 Variation of the vapour pressure of the compounds with the Fig. 16 Variation of the heat of vaporization of the different species
temperature. with the temperature.
Thermal conductivity
Liquid heat capacity
The thermal conductivity was calculated by eqn (A.12) using the
The correlation for the heat capacity of a liquid is a series
constants presented in Table 14.100
expansion in temperature, given by eqn (A.10).
l = A + BT + CT 2 + DT 3 + ET 4 (A.12)
C p = A + BT + CT 2 + DT 3 + ET 4 (A.10)
-1 -1
with l (W m K ) and T/K.
with C p (J kmol-1 K-1 ) and T/K, with exception for the ethyl The coefficients for each chemical compound for all the cor-
lactate species where C p is given in J mol-1 K-1 . relations presented in this appendix were based on appropriate
The liquid heat capacity as a function of temperature was experimental data available in the literature, with the exception
estimated by the above equation (Fig. 15), using the constants of the Gunn–Yamada method to estimate the molar volume,
presented in Table 12. since this is based on the corresponding-states principle.
Heat of vaporization
Acknowledgements
The correlation selected for the calculation of the heat of
The authors acknowledge financial support provided by
vaporization as a function of temperature is given by eqn
Fundação para a Ciência e a Tecnologia (Portugal) through
(A.11).100
the project PPCDT/EQU/61580/2004 and post-doctoral grant
SFRH/BPD/71358/2010 of C.S.M. Pereira.
DH V = A ⎡⎣1−T r ⎤⎦(B +CT r +DT r )
2
(A.11)
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