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Kinetics, Catalysis, and Reaction Engineering

Kinetic study of homogeneous catalyzed esterification
of series of aliphatic acids with different alcohols
Abha Sahu, and Aniruddha Bhalchandra Pandit
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.8b04781 • Publication Date (Web): 24 Jan 2019
Downloaded from http://pubs.acs.org on January 26, 2019

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Page 1 of 33 Industrial & Engineering Chemistry Research

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3 1 Kinetic study of homogeneous catalyzed esterification of series of aliphatic acids with
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6 2 different alcohols
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9 3 Abha Sahu1, Aniruddha B. Pandit 1*
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15 5 1Chemical Engineering Department, Institute of Chemical Technology, Mumbai 400019,
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18 6 India.
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53 17 *Author to whom correspondence should be addressed
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56 18 Email: ab.pandit@ictmumbai.edu.in, dr.pandit@gmail.com; Tel: +91-22-3361 2012; Fax:
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58 19 +91-22-33611020
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60 20

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1
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3 1 Abstract:
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2 The kinetic study of esterification of series of aliphatic carboxylic acid (C1-C5) with various
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9 3 alcohols (n-propanol, isopropanol, and n –butanol) have been conducted using sulphuric acid
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11 4 as a catalyst in batch experiments. Effects of variables such as reaction temperature, catalyst
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13 5 loading and initial mole ratio of reactants were investigated in detail. Temperature
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16 6 dependence reaction rates and activation energies were determined by the Arrhenius plot.
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18 7 Impact and reactivity of the series of linear chain length of carboxylic acids on esterification
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20 8 reactions were investigated in terms of steric and polar effects of the α substituents on the
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23 9 carboxylic group.
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26 10 Keywords: Esterification, homogeneous system, acid catalyst, sulphuric acid, kinetic model,
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28 11 activation energy, frequency factor, Taft equation and Charton correlation.
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31 12 1. Introduction:
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34 13 In the chemical industry, esterification is an essential chemical reaction. Esters are one of the
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37 14 main classes of chemicals and have many applications in various fields such as plasticizers,
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39 15 solvents, intermediates, and in pharmaceuticals industries. Esters are colorless, pleasant
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41 16 aroma that is responsible for the fragrance of fruits and flowers and volatile liquids. Because
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17 of the broad applications of esters in the chemical and allied fields, more than 500
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46 18 commercial esters exists. Esters are synthesized from simple hydrocarbons, and the chemical
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48 19 structure is R-COOR’. The general method for the preparation of esters is heating of
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50 20 carboxylic acid with alcohol; removing water from the reaction mixture 1-4. The general
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53 21 reaction for esterification is as given below:
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56 22
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1
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3 1 Typically esterification reaction is prolonged and shows limited conversion; in the absence of
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6 2 a catalyst, it requires many days to reach the equilibrium. For accelerating the higher
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8 3 conversion or reaction rate, acid catalysts are always used as a proton donor in liquid phase
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10 4 esterification 5,6. Due to the presence of by–product water, esterification reaction is extremely
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5 reversible and show second-order reactions kinetics. Presence of water (by-product) in the
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15 6 esterification reaction reduces the conversion of acid because of the hydrolysis reaction of the
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17 7 ester to acid and alcohol as it is a readily reversible reaction. This problem is surmounted by
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8 continuous removal of by-product water through distillation, using dean stark methods, using
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22 9 a molecular sieve to absorb water or any advance separation technique such as reactive
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24 10 distillation 3,7. The primary challenge with esterification reaction in the absence of a catalyst
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26 11 is that it requires several days to acquire equilibrium due to the reversibility and low reaction
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29 12 rate, showing the limited equilibrium conversion of acid. Therefore, in the esterification rate
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31 13 of reaction is enhanced by using a catalyst. Heterogeneous and homogeneous acids play the
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33 14 role of the catalyst which protonate the oxy group of carboxylic acid and is the rate-
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15 determining step in the esterification reaction mechanism.[5,8] A homogeneous catalyst for
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38 16 example acid catalyst that acts as a proton donor and is used to enhance esterification
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40 17 reaction. Mineral acid for example H2SO4, HI, and HCl and an organic acid such as p-
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18 Toluene sulfonic acid are commonly employed as homogeneous catalyst. The varying
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45 19 reaction conditions, such as the elevated temperatures, increase in the mole ratio of alcohol to
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47 20 acid and employing of more active catalyst enhance the reaction rate in the presence of a
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49 21 catalyst 6,8.
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52 22 Mineral acid catalyst has many drawbacks such as being corrosive in nature and difficult to
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54 23 separate yet they are of low cost, high solubility gives high conversion and is having a high
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56 24 density of acid sites making it preferable over heterogeneous catalysts 2. Sulphuric acid is
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25 commonly used as a homogeneous catalyst in the esterification reaction of acid and alcohol
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1
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3 1 because of its strong acid strength and robust dehydrated nature. The acid strength of a
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6 2 mineral acid is responsible for the protonation of the acid. In the literature, a comparative
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8 3 study of heterogeneous and homogeneous catalyzed esterification reaction has been done.
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10 4 The present study reports higher conversion of series of aliphatic acids to esters using
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5 sulphuric acid as a homogeneous catalyst and is compared the activation energy with
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15 6 heterogeneous catalyzed reaction reported in the litrature. In general, due to the presence of
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17 7 free protons, reaction mixture using homogeneous catalysts (liquid-liquid phase) results in
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8 faster reaction rates as compared to heterogeneous (liquid-solid reaction mixture) catalyst 8.
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22 9 The objective of the current work is to examine the esterification of series of aliphatic acid
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24 10 (C1-C5) with three different alcohols, n-propanol, isopropanol, and n –butanol using
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26 11 sulphuric acid as a catalyst.
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29 12 The manuscript reports first of its kind study of esterification of series of a carboxylic acid
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31 13 (formic, acetic, propionic, butyric and pentanoic acid) with different alcohols (n-propanol,
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33 14 isopropanol and n-butanol respectively) using sulphuric acid as a homogeneous catalyst. The
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15 present study also elaborate the structural effects and the reactivity of carboxylic acids and
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38 16 effect of length and branching of alcohols for homogeneously catalyzed esterification
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40 17 reaction of series of a carboxylic acids. The earlier literature has reported limited work on
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18 esterification of series of such a carboxylic acids with various alcohols using a heterogeneous
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45 19 and homogeneous catalyst. In the earlier literature, the esterification of acrylic, acetic,
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47 20 propionic and butyric acid but not with formic and pentanoic acid, with methanol, ethanol,
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49 21 and propanol were studied using hydrogen chloride and hydrogen iodide as a catalyst but not
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52 22 sulphuric acid 5. Also, the past litrature reported esterification of such a series of carboxylic
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54 23 acids with methanol, ethanol and propanol but not with n-propanol, isopropanol and n-
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56 24 butanol under identical experimental conditions 5,9. The impact of chain length of various
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25 carboxylic acids (acetic, propionic, butyric, hexanoic and caprylic acids) with methanol
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1
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3 1 employing sulphuric acid and SAC-13 ( a Nafion/silica nanocomposite ) as a catalyst has
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6 2 been investigated and reported but not with formic and pentanoic acid9. The present work
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8 3 endeavored to examine the esterification of formic, acetic, propionic, butyric and pentanoic
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10 4 acid with propanol, isopropanol, and n –butanol respectively using sulphuric acid as a
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5 homogeneous catalyst in the batch reactor. In the present research, a series of esterification
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15 6 reaction of variable length of carboxylic acid have been conducted to find out the effect of
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17 7 various reaction parameters, viz. reaction temperature, the mole ratio of reactants (acid :
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8 alcohol) and the catalyst loading. Moreover, the latter part of this paper also presents the
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22 9 kinetic modelling of the esterification reaction and reactivity of carboxylic acids and alcohol
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24 10 under the optimized reaction conditions.
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26 11 The literature is, limited to only a couple of studies found which elaborate the structural
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29 12 effects and the reactivity of carboxylic acids for homogeneously catalyzed esterification
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31 13 reaction 5,9. In contrast, the present study reveals the correlation between chemical reactivity
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33 14 and chemical structure for various length alkyl chain carboxylic acids and their bulkier and
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15 larger counterparts using a homogeneous catalyst (sulphuric acid) with propanol, isopropanol,
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38 16 and n –butanol respectively.
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40 17 2. Experiments:
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18 2.1. Materials:
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45 19 Propanol, isopropanol, and n –butanol analytical grade with purity of 99.5% were purchased
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47 20 from HiMedia Lab. Pvt. Ltd (Mumbai, India).The homogeneous catalyst, sulphuric acid with
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49 21 a purity of 99% and specific gravity of 1.853g/c.c., molecular seive were supplied by Thomas
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52 22 Bakers, Mumbai, India. Formic acid, acetic acid, propionic, butyric acid and pentanoic were
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54 23 supplied by SDFCL Mumbai, India. All the reagents used in the experiments were of
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56 24 analytical grade.
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59 25
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1
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3 1 2.2. Methods:
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6 2 Experiments were conducted in a three neck round bottom flask batch reactor of a capacity of
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8 3 250 ml with a magnetic stirrer. A reflux condenser was equipped at the top of the reactor to
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10 4 stop the escape of volatile compounds. The reactor was charged with the carboxylic acid
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5 and respective alcohol followed by the addition of sulphuric acid as a catalyst. The required
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15 6 amount of reagents was calculated by mole ratio for each reaction. The stirring rate of
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17 7 magnetic stirrer was kept constant at 650 rpm throughout the experiments. The effects of the
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8 catalyst (H2SO4) loading to the percentage weight of acids, the mole ratio of acids to alcohols
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22 9 and the variation of temperature were studied for all acid- alcohol combination. The length of
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24 10 carbon chain is different and their miscibility in alcohols and boiling points are different for a
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26 11 series of an acid. Therefore, to get the maximum conversion of acids to esters different
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29 12 temperature ranges were studied. The by-product, water was adsorbed by means of a
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31 13 molecular sieve. A Type 3A molecular sieve was used to adsorb by-product, water molecule
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33 14 from the reaction mixture. Molecular sieves are usually zeolite compounds that strongly
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15 adsorb water molecules as they have carefully controlled pore sizes. While both water and the
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38 16 solvent will adsorb strongly to the surface of molecular sieve, but the pores present on large
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40 17 surface area of molecular sieve is only accessible to the smaller molecules like water, and
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18 they are effectively adsorbed and removed from the reaction mixture among the solvent
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45 19 either in a vapour or liquid form. The aliquots were pipetted out at regular time intervals of
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47 20 30 minutes and were monitored by gas chromatographic analysis.
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50 21 For analysis of acids and esters gas chromatography (Chemito, GC 8610) was used using
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22 hexane as an internal standard. The analyzing conditions for gas chromatograph analysis
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55 23 were as follows: a flame ionisation detector (FID), a stainless steel column (packed column)
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57 24 with the stationary phase of 3% SP-2310 and 2% SP-2300 matrix 100/120 Chromosorb solid
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1
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3 1 support. The detector temperature was 230°C; injection temperature was 210°C with nitrogen
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6 2 as a carrier gas.
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8 3 3. Results and discussion:
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11 4 The probable reaction parameters which affect the rate of esterification reaction to increase
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13 5 the conversion of acids to esters were studied in detail. The variables were reaction
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16 6 temperature, catalyst loading, and reactants (acid: alcohol) mole ratio. The experiments were
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18 7 performed by changing various process parameters. The activation energy, frequency factor,
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20 8 and coefficient of variance were calculated at various temperatures for series of a carboxylic
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23 9 acid (C1-C5) with n-propanol, isopropanol, and n-butanol respectively.
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26 10 3.1. Effect of mole ratio:
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28 11 Esterification reaction of acid with alcohol is equilibrium – limited, reversible reaction and
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30 12 the conversion of acid can be enhanced by removing, by-product water or using an excess of
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33 13 either of the reagents 8. In the present study, the effects of mole ratio of acids to alcohols were
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35 14 investigated. Four different mole ratios of alcohols to acids were studied to find out the effect
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37 15 of initial mole ratio on maximum conversion of series of aliphatic acids while other
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16 parameters such as reaction temperature and catalyst loading were kept constant. Increasing
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42 17 the mole ratio of respective acid to alcohol increases the conversion of acids. The
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44 18 esterification of acetic acid with n-propanol, isopropanol and n-butanol using H2SO4 as a
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19 catalyst increases the conversion of acid from 62.2 ± 0.06 % to 95.2 ± 0.17 %, 58.8 ± 0.04 %
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49 20 to 92.6 ± 0.17 % and 60.07 ± 0.05 % to 93.7 ± 0.17 % respectively with increasing the mole
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51 21 ratio from 1:1to 1:4 (acid: alcohol) shown in fig.1a-1c over a similar time interval (240
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53 22 minute). Similarly, conversion of formic, propionic, butyric and pentanoic acids increased
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56 23 with an increasing the mole ratio of acid to alcohol from 1:1 to 1:3, 1:4, 1:4 and 1:6
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58 24 respectively as shown in fig. 2 a-2d. However, it was found that for esterification of formic
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60 25 acid, the conversion of formic acid at a mole ratio of 1:4 is slightly lower than 1:3 (96 ± 0.18

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1
2
3 1 % to 95.2 ± 0.18 %, 93.5 ± 0.15 % to 92.6 ± 0.15 % and 94.1 ± 0.18 % to 93.2 ± 0.15 %)
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6 2 with n-propanol, isopropanol, and n-butanol respectively. For acetic acid the conversion of
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8 3 acids is slightly higher from 1:3 to 1:4 mole ratio( 91.4 ± 0.11 % to 95.2 ± 0.17 %, 91.2 ±
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10 4 0.17 % to 92.6 ± 0.17 % and 92.9 ± 0.17 % to 93.7 ± 0.17 % with n-propanol, isopropanol
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12
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5 and n-butanol respectively) as shown in fig.1a-1c..The reason could be the dilution of
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15 6 alcohols concentration at higher mole ratio. Therefore, a decrease in conversion or slightly
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17 7 increase in conversion were obtained for high mole ratio 3.
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20 8 Increase in the mole ratio of acids to alcohols for propionic acid, butyric acid, and pentanoic
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23 9 acid (1:1 to 1:4 and 1:6) leads to a significantly enhance the conversion of respective acid.
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25 10 The results obtained for the effect of mole ratio on the carbon chain length of a carboxylic
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27 11 acid to n-propanol, isopropanol and n-butanol respectively specified that with the use of an
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12 excess of alcohol, the equilibrium conversion of respective acid can be efficiently enhanced.
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32 13 The results are illustrated in the Supporting Information (Table S1). From fig.1a-1c and 2a-2d
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34 14 it can be concluded that the initial mole ratio of acids to alcohols has significant impact on
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36 15 the equilibrium conversion of respective acid, which notably increases with using excess
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39 16 alcohols and equilibrium conversions shifted towards the desired product. Further increase in
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41 17 the moles of alcohols has a little effect on the reaction rate; it only causes to attain the state of
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43 18 equilibrium in the somewhat shorter period 1,8. The maximum percentage conversion of series
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46 19 of carboxylic acids (C1-C5) with n-propanol, isopropanol and n-butanol respectively, were
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48 20 optimised and reported in the Supporting Information (Table S1).
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51 21 3.2. Effect of concentration s of catalyst:
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53 22 The amount of catalyst loading is the most important parameter to increase the equilibrium
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56 23 conversion of acid and the rate of the reaction because catalyst provides an alternative path
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58 24 by lowering the activation energy of the reaction and giving out the desired product. Hence, it
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60 25 consequently increases the reaction rate and higher conversion 1,8. To evaluate the effect on

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1
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3 1 the amount of catalyst, experiments were performed by varying the catalyst concentration
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6 2 based on the weight of the acids from 0.5% to 7% w/w keeping the temperature and mole
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8 3 ratio of acids to alcohols constant. It was found that the conversion of a variable length of
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10 4 carbon chain of a carboxylic acid with n-propanol, isopropanol, and n-butanol respectively
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5 are efficiently increased with increasing the catalyst loading as shown in the fig. 3a-3c for
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15 6 esterification of acetic acid. The higher conversion of acids with a high concentration of
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17 7 catalyst is due to the presence of more H+ ions which eventually enhances the rate of reaction
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19 8.
8 Esterification of formic, acetic, propionic, butyric and pentanoic acids were significantly
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22 9 increased and attain equilibrium conversion. From fig. 3a-3c and 4a it is indicated that further
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24 10 increase in the amount of catalyst from 3% to 5% the conversion of formic acids decreases
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26 11 from 96.0 ± 0.18 % to 94.7 ± 0.18 % , 93.5 ± 0.15 % to 92.2 ± 0.15 % and 94.1 ± 0.18 % to
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29 12 93.2 ± 0.15 %. And for acetic acid conversion decreases from 95.2 ± 0.17 % to 94.3 ± 0.18
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31 13 %, 92.6 ± 0.17% to 91.7 ± 0.17 % and 93.7 ± 0.17 % to 93 ± 0.17 % with n propanol,
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33 14 isopropanol and n-butanol respectively. The equilibrium conversion of formic and acetic acid
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15 reduces when the amount of catalyst concentration increases from 3 to 5% by weight of acids.
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38 16 This might be due to the dehydration of alcohols in the presence of excess of acid catalyst
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40 17 resulting in the alkene formation (n-propene, isopropene and n-butene) as shown in scheme1
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42 10.
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53 19
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56 20 Scheme1. Dehydration of alcohol in the presence of excess acid catalyst
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1
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3 1 Fig. 4b-4d depicted the conversion of propionic,butyric and pentanoic acids increased with
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6 2 increasing the catalyst amount from 0.5 % to 5 % and 1 % to 7 % respectively. In fig. 3a-3c
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8 3 the graph shows the effect of catalyst loading on the esterification reaction of acetic acid acid
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10 4 with n-propanol, isopropanol, and n-butanol respectively. It can be concluded that the rate of
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12
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5 equilibrium conversion of respective acid increases with an increasing in the catalyst
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15 6 concentration. This is because increase in the number of H+ ions in the reaction mixture and
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17 7 hence more active free protons are available which is proportional to the used catalyst
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8 concentration 7. Thus in the presence of more H+ ions a higher number of carbonyl carbon of
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22 9 acids are activated, and nucleophilic attack by alcohols become more favourable resulting in
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24 10 desired products 11. Fig. 3a-3c and 4a-4d reveals that the catalyst concentrations of 3% for
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26 11 formic and acetic acids, 5% for propionic acid and 7% for butyric and pentanoic acids by
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29 12 weight of the acids resulted in a relatively higher conversion. It is because of the 3%-7%
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31 13 catalyst concentration by weight of acids are the maximum amount of catalyst required to
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33 14 activate the carbonyl carbon of various chain length of carboxylic acids 12. Therefore the
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15 amount of 3 %, 5 % and 7% catalyst concentrations by weight of the acids are considered as
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38 16 more efficient for the esterification system of various carboxylic acids involving n-propanol,
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40 17 isopropanol, and n-butanol respectively.
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43 18 3.3 Effect of Temperature:
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46 19 The effect of reaction temperature on the rate of reaction is extremely imperative as this
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48 20 information helps in calculating the rate constant of the reaction and the activation energy.
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50 21 Hence the rate constant, activation energy and frequency factor are functions of temperature.
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22 The conversion and rate of reaction enhances with increasing the temperature are due to the
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55 23 more successful collision which has sufficient energy to break the bonds resulting in the
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57 24 product 7,8.
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3 1 Esterification reactions are conducted at various temperatures to examine the effect of
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6 2 temperature on the reaction rate while keeping other parameters constant. The reaction was
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8 3 conducted with four different temperatures for fix mole ratio of respective acid to alcohol and
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10 4 catalyst concentration. Fig. 5a-5c showed the esterification of acetic acid. The effect of
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5 temperature on the esterification of acetic acid was investigated over a temperature range of
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15 6 323.15 K to 353.15 K at 1: 4 mole ratio of acid to alcohols (acetic acid: n-propanol,
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17 7 isopropanol, and n-butanol) and catalyst concentration(H2SO4) of 3% w/v to acid (240
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19
8 minute). Similarly, esterification of formic, propionic and butyric acids with n-propanol,
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22 9 isopropanol and n-butanol were investigated at different temperature region with molar ratio
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24 10 of 1:3 and 1:4 (acids: alcohols ) , catalyst loading of 3%, 5% and 7 % w/v of acid (300
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26 11 minute) . Esterification of pentanoic acid with n-propanol, isopropanol and n-butanol were
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29 12 carried out over 7% w/v of the catalyst over a temperature range of 363.15 K to 383.15 K
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31 13 with a mole ratio of 1:6 (acids: alcohols) over fix time period (300 minute) to get the
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33 14 maximum equilibrium conversion. Results are shown in fig. 5a-5c indicate that the
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15 conversion of acids and rate of reactions are sensitive to the change in the reaction
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38 16 temperature. Also, the change in the temperature affects the kinetics and thermodynamics of
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40 17 the reaction. In order to find out the scope of the present work the esterification of other
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18 carboxylic acids (formic, propionic, butyric and pentanoic acid) were examined. The detailed
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45 19 graphs (S1a-S1d) are included in the Supporting Information file in the revised manuscript.
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48 20 3.4. Evaluation of kinetic parameter:
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50 21 The kinetic model of the esterification reaction between acid and alcohol to produce ester and
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52
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22 water is reversible and elementary second order reaction; first order with respect to each
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55 23 reactant. To develop a kinetic model esterification reaction is expressed as:
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57 24
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59 25 𝐴 + 𝐵 ⇋ 𝐸 + 𝑊 (2)
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1
2
3 1 Where 𝐴 = Acid, 𝐶𝐴 = concentration of acid
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6 2 𝐵 = Alcohol, 𝐶𝐵 = concentration of alcohols
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8 3 𝐸 = Ester, 𝐶𝐸 = concentration of esters
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11 4 𝑊 = Water, 𝐶𝑊 = concentration of water
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13 5 At stoichiometric condition rate of equation can be formulated as:
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15 6
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18 7 ― 𝑟𝐴 = 𝑘1 𝐶𝐴𝐶𝐵 ― 𝑘2 𝐶𝐸𝐶𝑊 (3)
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20 8
21
22
9 However, in the present work, the excess of alcohols was used and the water was adsorbed by
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24
25 10 means of molecular sieve from the reaction mixture during the reaction, hence reverse
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27 11 reaction could be neglected and it was considered that the reaction equilibrium did not hinder
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29 12 the completion of the reaction. Furthermore, the excess of alcohol was used in the reaction,
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32 13 therefore, its concentration could be assumed to remain constant during the reaction time.
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34 14 Therefore the pseudo-homogeneous first-order kinetic model was proposed as the reaction
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36 15 mechanism and is expressed by the following equation:
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38
39
16 𝑘 𝑡 = ― ln (1 ― 𝑋𝐴) (4)
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41 17
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43 18 In fig. 6a., 6c. and 6d. the graph was plotted between ― ln (1 ― 𝑋𝐴) versus time in minute to
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46 19 find out the rate constant. The kinetic data obtained fitted well for a proposed kinetic model
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48 20 (pseudo homogeneous first order) and was appropriate with high regression coefficients
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50 21 (Table 1).
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53 22
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55 23 3.5. Apparent Activation Energy Measurement
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1
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3 1 The reaction rate constant was obtained using linear regression method using the equilibrium
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5
6 2 equation and integrated rate equation ( graph between ― ln (1 ― 𝑋𝐴) versus time). It was
7
8 3 utilized to find out the value of rate constant, activation energy (Ea) and frequency factor (A),
9
10 4 expressed by Arhhenius equation. To find out the value of frequency factor and activation
11
12
13 5 energy, a graph is plotted between lnk verses 1/T as shown in fig 6b., 6d. and 6f. 1,3,11. It was
14
15 6 found that the activation energy for the esterification of acetic acid with n-propanol,
16
17 7 isopropanol, and n-butanol are 36.27, 33.51 and 34.69 kJ/mole respectively, which was quite
18
19
20 8 comparable to reported in the literature.[13-17] For propionic acid the, activation energy were
21
22 9 found 36.34, 35.33 and 35.93, for butyric acid the value of activation energy were found
23
24 10 35.59, 36.12 and 34.79 kJ/mole respectively and was comparable to those reported in the
25
26
27
11 previous literature 4,18-20. In spite of relatively similar results the, mole ratio of respective acid
28
29 12 to alcohol, catalyst loading and temperature in our experiments were different than those
30
31 13 described in the literature.
32
33
34 ― 𝐸𝐴
35 14 𝑘 = 𝑘0 exp ( 𝑅𝑇 ) (5)
36
37
38 𝐸𝐴
15 ln [𝑘] = ln [𝑘0] ― 𝑅𝑇 (6)
39
40
41
42 16 The activation energy, frequency factor and coefficient of regression for a series of a
43
44 17 carboxylic acid with n-propanol, isopropanol, and n-butanol respectively are summarised
45
46
18 (Table 1) . The linear plot between ― ln (1 ― 𝑋𝐴) versus time for the esterification of formic,
47
48
49 19 propionic, butyric and pentanoic acid with n-propanol, isopropanol and n-butanol are
50
51 20 reported in the Supporting Information (S2a-S2c, S3a-S3c, S4a-S4c and S5a-S5c). And detail
52
53
54
21 of graph plotted between lnk verses 1/T for the esterification of formic, propionic, butyric and
55
56 22 pentanoic acid with n-propanol, isopropanol and n-butanol are in the Supporting Information
57
58 23 (S6a-S6c, S7a-S7c, S8a-S8c and S9a-S9c).
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2
3 1
4
5
6 2
7
8
3 Table 1. Value of activation energies, frequency factor, coefficient of determinates and
9
10 4 TOF for esterification of various carboxylic acids with n-butanol, isopropanol and n-
11
12 5 butanol respectvely.
13
14
15
Sr.N. Esters Activation Frequency R2 TOF (h-1)
16 energy Factor
17 (kj/mol) (min.-1)
O

18 1 33.02 1822 0.957 22.86

19 H O

20 O
3a
21 2 33.13 1680 0.998 22.26
H O
22
3b
23 O

24
3 34.11 2456 0.998 22.38
H O
25
26 O
3c
27 4 O
36.27 2869 0.991 12.93
28
29 3d
O
30 5 33.51 982 0.995 12.58
31 O

32 O
3e
33 6 O 34.69 1559 0.995 12.73
34
35 O
3f
36 7 O
36.34 1927 0.978 6.26
37
38 O
3g
39 8 35.33 1276 0.996 6.06
40 O

41
3h
42 O

43 9 O
35.93 1632 0.996 6.14
44
45
3i O

46 10 O
35.59 795 0.993 2.94
47
48
3j O

49 11 36.12 936 0.989 2.89

O

50 3k
51 O

12 34.79 584 0.989 2.92

52
O

53 3l
54
O

13 37.36 1003 0.989 2.53

55
O

56 3m O

57 14 O
36.98 873 0.992 2.52
58
59 3n
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2
3 15
O

O 35.07 459 0.989 2.47

4
5 3o
6 1
7
8
9 2 3.6. Reactivity of carboxylic acids:
10
11
12
3 The impact of chain length of various carboxylic acids (formic, acetic, propionic, butyric and
13
14
15 4 pentanoic acid) on the esterification reaction with n-propanol, isopropanol, and n-butanol
16
17 5 respectively at optimal reaction conditions were studied. Fig 7a-7c, shows the effect of
18
19 6 various chain length of carboxylic acids on the esterification reaction with n-propanol,
20
21
22 7 isopropanol, and n-butanol respectively at 343.15 K for formic, acetic, propionic, butyric, and
23
24 8 pentanoic acids, the mole ratio of 1:3 and catalyst loading 3% for fix time (180 minute). The
25
26 9 conversion of acids decreases from 96 ± 0.18 % to 33.9 ± 0.11%, 93.5 ± 0.15 % to 31.2 ±
27
28
29
10 0.12 % and 94.1 ± 0.18 % to 31.5 ± 0.12 % as the increases in the chain length of carboxylic
30
31 11 acids for n-propanol, isopropanol, and n-butanol respectively as shown in fig. 7a-7c. Table 1 ,
32
33 12 reveal the reactivity difference in term of turn over frequency (TOF) of the series of
34
35
13 carboxylic acids with n-propanol, isopropanol, and n-butanol respectively using sulphuric
36
37
14 acid as catalyst at optimized reaction condition for all experiments 5,9. It was evaluated that
38
39
40 15 the reactivity of the carboxylic acid decreases with increasing the alkyl chain length for each
41
42 16 addition of each CH2 moiety. Two factors namely steric hindrance and an inductive effect
43
44
45 17 contribute to the diminishing reactivity of carboxylic acids. With the lengthening of the alkyl
46
47 18 chain of the acids, the electrophilicity of the carboxylic group decreases due to the inductive
48
49 19 effect. Hence in the rate controlling step, the nucleophilic attack on carbonyl carbon become
50
51
52
20 more energy hindered 9.
53
54
55 21 The decisive factor is responsible for the steric component which affects the reactivity of the
56
57 22 carboxylic acid in acid catalyzed esterification. With an increase in molecular size, the steric
58
59 23 hindrance increases which results in electronic repulsion in reactant molecules between non
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3 1 bonded atoms. Due to this repulsive steric hindrance, in the intermolecular region the electron
4
5
6 2 density diminishes and affects the molecule bonding interaction. Thus the steric effect
7
8 3 increases with an alkyl chain of carboxylic acids. Since the steric effects are governed by
9
10 4 molecular size and preferential conformations called conformational leveling effect. In
11
12
13
5 homogeneously catalyzed esterification reactions higher carboxylic acid may assume a
14
15 6 conformation which minimizes the contribution of steric hindrance. Because of the free acid
16
17 7 sites present in reaction mixture in the homogeneously catalyzed esterification reaction, the
18
19
8 steric hindrance is less important as compared to a heterogeneous catalyst which has fixed
20
21
22 9 acid sites 5,9.
23
24
25 10 The steric effect caused by the alpha substituents in the carbon atom of aliphatic system was
26
27 11 quantitatively calculated by using Taft equation, the correlation shown below in equation
28
29
30
12 (12).
31
32
33 13
34
35
36
37
14 log (𝑟 𝑟 )
0
= 𝛿 𝐸𝑠 (12)
38
39
40 𝑟
15 Where 𝑟0 represents the rate constant of an acid having a given alpha substituent versus
41
42
43 16 acid bearing a methyl group, 𝐸𝑠 is the steric hindrance and 𝛿 is the susceptibility
44
45
46 17 measurement of steric effect of substituents for a particular reaction series. Further Taft
47
48 18 correlation was improved by Chatron and 𝐸𝑠 constant was replaced by vander waals radii 𝑣
49
50
19 for a given substituents 9. The proposed Charton correlation is shown in equation 13.
51
52
53
54 20 log 𝑟 = 𝜑𝑣 + ℎ (13)
55
56
57 21 Where 𝜑 and ℎ are constants. The values of 𝑣 for homogeneous catalysed esterification
58
59 22 reaction have been determined in literature 21. In fig. 8a-8c, graph plotted between log TOF
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3 1 vs 𝑣 suggests that the steric effect is dominate for catalytic activity in homogeneous catalysed
4
5
6 2 esterification reaction.
7
8
9 3 In fig. 8a-8c, graph is plotted between log (TOF) vs 𝑣, for acetic, propionic, butyric and
10
11 4 pentanoic acid with n-propanol, isopropanol and n-butanol respectively. Results indicated
12
13
5 that the reactivity of acids depends on stearic hindrance of acids. As carbon chain length of
14
15
16 6 acids increases stearic hindrance also increases and the reactivity of acids decreases as shown
17
18 7 in fig. 8a-8c. However the reactivity of formic acid is independent of stearic hindrance as it is
19
20 8 not mention in graph, but value of TOF for formic acid listed in Table1. At same point fig.8
21
22
23 9 (a-c) and are seem to be identical for the esterification of series of acids with n-propanol,
24
25 10 isopropanol and n-butanol respectively. Fig. 8 (a-c) reveals that the reactivity of series of
26
27 11 acids with different alcohols only marginally depends on the physical property i.e. solubility
28
29
30
12 and boiling of different alcohols (n-propanol, isopropanol and n-butanol respectively) instead
31
32 13 of chemical property (steric hindrance and inductive effect) at the same temperature. Hence
33
34 14 the curves (a–c) in Figure 8 seems be identical for esterification of series of acids with all
35
36
15 alcohols (n-propanol, isopropanol and n-butanol respectively) are seem to be identical 22.
37
38
39
40
16 3.7. Reactivity of alcohols:
41
42
43 17 The impact of chain length and branching of various alcohols (n-propanol, isopropanol, and
44
45 18 n-butanol) were studied by conducting multiple experiments with formic, acetic, propionic,
46
47 19 butyric and pentanoic acids using sulphuric acid as a catalyst. Fig. 9 reveals that the
48
49
50 20 conversion of acetic acids with increasing chain length and branching of alcohols. The
51
52 21 equilibrium conversion of acetic acid after fix time (240 minute) was observed to be 95.2 ±
53
54 22 0.17%, 92.6 ± 0.17 % and 93.7 ± 0.17% with n-propanol, isopropanol, and n-butanol
55
56
57
23 respectively. From fig. 9, it can be concluded that, for a given catalyst the conversion of
58
59 24 acetic acids are highest for n-propanol, n –butanol and isopropanol respectively. Similarly for
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3 1 formic, propionic and butyric acid the order of reactivity of alcohol is n-propanol, n –butanol
4
5
6 2 and isopropanol respectively. The order of reactivity of alcohol is n-propanol, isopropanol
7
8 3 and n-butanol respectively for pentanoic acid. Due to steric hindrance, both long chain and
9
10 4 branching cause the decreases in the acids conversion.
11
12
13 5 4. Conclusions:
14
15
16
17
6 Based on the results obtained from the experiments the kinetics of homogeneously catalyzed
18
19 7 esterification of different carbon chain length of aliphatic carboxylic acids with n-propanol,
20
21 8 isopropanol, and n-butanol were evaluated. The resultant kinetics data were well correlated
22
23
9 with pseudo homogeneous first order reaction for all the experiments. The conversion of
24
25
26 10 acids and rate constant were found to increase with increasing the temperature, initial
27
28 11 respective acid: alcohol mole ratio and the catalyst loading. For different carboxylic acids
29
30 12 conversions obtained were the highest for formic acid followed by acetic, propionic, butyric
31
32
33 13 and pentanoic acid respectively. Among the alcohols the order of reactivity was found to be
34
35 14 n-propanol > n-butanol> isopropanol for the esterification of formic, acetic, propionic and
36
37 15 butyric acids. For the esterification of pentanoic acid order of reactivity of alcohols were n-
38
39
40
16 propanol > isopropanol > n-butanol. To achieve 100 % conversion one has to make use of an
41
42 17 in situ separation technique such as reactive distillation.
43
44
45 18 Acknowledgement:
46
47
48 19 We gratefully acknowledge the University Grant Commission (F.5-64/2007 BSR), New
49
50 20 Delhi, India for financially supporting the research work.
51
52
53
54
21 Supporting Information:
55
56
57 22 The detail plot for effect of temperature on esterification of formic, acetic, propionic, butyric
58
59 23 and pentanoic acids are shown in fig. S1a-S1d. And linear plot between ― ln (1 ― 𝑋𝐴) versus
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2
3 1 time and lnk verses 1/T for esterification of formic, acetic, propionic, butyric and pentanoic
4
5
6 2 acids are shown in fig. (S2a-S2c, S3a-S3c, S4a-S4c and S5a-S5c ) and (S6a-S6c, S7a-S7c,
7
8 3 S8a-S8c and S9a-S9c).
9
10
11 4 References:
12
13
14 5 [1] Mittal, A.; Nair, S.; Deshmukh, K. The Kinetic Comparison Study of Catalytic
15
16
17
6 Esterification of Butyric Acid and Ethanol over Amberlyst 15 and Indion-190 Resins.
18
19 7 IJIRSET 2015, 5860–5867.
20
21
22 8 [2] Beula, C.; Sai, P. S. T. Kinetics of Esterification of Acetic Acid and Ethanol with a
23
24 9 Homogeneous Acid Catalyst. Indian Chem. Eng. 2015, 57 (2), 177–196.
25
26
27 10 [3] Zeki, N. S. A.; Al-Hassani, M. H.; Al-Jendeel, H. A. Kinetic Study of Esterification
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29
30 11 Reaction. Al-Khwarizmi Eng. J. 2010, 6 (2), 33–42.
31
32
33 12 [4] Ali, S. H.; Tarakmah, A.; Merchant, S. Q.; Al-Sahhaf, T. Synthesis of Esters:
34
35 13 Development of the Rate Expression for the Dowex 50 Wx8-400 Catalyzed Esterification of
36
37
14 Propionic Acid with 1-Propanol. Chem. Eng. Sci. 2007, 62 (12), 3197–3217.
38
39
40
41
15 [5] Keshav, A.; Joshi, N. Experimental Study of Esterification of Carboxylic Acid with
42
43 16 Different Alcohol Using Various Catalysts. IJSEM 2018, 3 (1), 27–29.
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45
46 17 [6] Lilja, J.; Wärnå, J.; Salmi, T.; Pettersson, L. J.; Ahlkvist, J.; Grénman, H.; Rönnholm,
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48 18 M.; Murzin, D. Y. Esterification of Propanoic Acid with Ethanol, 1-Propanol and Butanol
49
50
51 19 over a Heterogeneous Fiber Catalyst. Chem. Eng. J. 2005, 115 (1–2), 1–12.
52
53
54 20 [7] Kong, P. S.; Aroua, M. K.; Raman, A. A. Kinetics Study of Esterification Reaction of
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56 21 2-Methyl-4-Chlorophenoxyacetic Acid (MCPA Acid). Int. J. Chem. React. Eng. 2011, 9 (1).
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3 1 [8] Jyoti, G.; Keshav, A.; Anandkumar, J. Experimental and Kinetic Study of Esterification
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6 2 of Acrylic Acid with Ethanol Using Homogeneous Catalyst. Int. J. Chem. React. Eng. 2016,
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8 3 14 (2), 571–578.
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10
11 4 [9] Lotero, Y. Liu, E.; Goodwin, J.G. Jr. effect of carbon chain length on esterification of
12
13 5 carboxylic acids with methanol using acid catalysis, J. Catal. 2006(243)221-228.
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6 [10] Altman, E.; Stefanidis, G. D.; Van Gerven, T.; Stankiewicz, A. Microwave-Promoted
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19 7 Synthesis of n-Propyl Propionate Using Homogeneous Zinc Triflate Catalyst. Ind. Eng.
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21 8 Chem. Res. 2012, 51 (4), 1612–1619.
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23
24 9 [11] Kusumaningtyas, R. D.; Ratrianti, N.; Purnamasari, I.; Budiman, A. Kinetics Study of
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10 Jatropha Oil Esterification with Ethanol in the Presence of Tin (II) Chloride Catalyst for
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29 11 Biodiesel Production. AIP Conference Proceedings 2017, 1788 (Ii).
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31
32 12 [12] Cardoso, A. L.; Neves, S. C. G.; da Silva, M. J. Esterification of Oleic Acid for
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34 13 Biodiesel Production Catalyzed by SnCl2: A Kinetic Investigation. Energies 2008, 1 (2), 79–
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36
37 14 92.
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39
40 15 [13] Mali, V. V.; Deosarkar, M. P. Esterification of Acetic Acid With Butanol in the
41
42 16 Presence of Solid Acid Catalyst. International Journal of Advances in Science Engineering
43
44 17 and Technology 2016, 4 (2), 245–248.
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46
47
18 [14] Gurav, H. R.; Nandiwale, K. Y.; Bokade, V. V. Pseudo-Homogeneous Kinetic Model
48
49
50 19 for Esterification of Acetic Acid with Propanol Isomers over Dodecatungstophosphoric Acid
51
52 20 Supported on Montmorillonite K10; 2014; Vol. 27.
53
54
55 21 [15] Tao, D.; Wu, Y.; Zhou, Z.; Geng, J.; Hu, X.; Zhang, Z. Kinetics for the Esterification
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57
58
22 Reaction of n -Butanol with Acetic Acid Catalyzed by Noncorrosive Brønsted Acidic Ionic
59
60 23 Liquids. 2011, 1989–1996.

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3 1 [16] Li, W.; Liu, W.; Xing, W.; Xu, N. Esterification of Acetic Acid and n - Propanol with
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6 2 Vapor Permeation Using NaA Zeolite Membrane. 2013.
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8
9 3 [17] Balasubramanian, K.; Kuriacose, J.C.; Kinetic of Reaction of Acetic acid and 2-
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11 4 Propanol Catalyzed by Zinc Chromium Ferrite Spinel. J. Res. Inst. Cata. Hokkaido Univ.
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13 5 (1983 (1), 53-60.
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15
16
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6 [18] Lee, M.-J.; Chiu, J.-Y.; Lin, H. Kinetics of Catalytic Esterification of Propionic Acid
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19 7 and n -Butanol over Amberlyst 35. Ind. Eng. Chem. Res. 2002, 41 (12), 2882–2887.
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21
22 8 [19] Santhanakrishnan, A.; Shannon, A.; Peereboom, L.; Lira, C. T.; Miller, D. J. Kinetics
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24 9 of Mixed Ethanol/ n -Butanol Esterification of Butyric Acid with Amberlyst 70 and p -
25
26
27
10 Toluene Sulfonic Acid. Ind. Eng. Chem. Res.2013, 52 (5), 1845–1853.
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29
30 11 [20] Ju, I. B.; Lim, H. W.; Jeon, W.; Suh, D. J.; Park, M. J.; Suh, Y. W. Kinetic Study of
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32 12 Catalytic Esterification of Butyric Acid and N-Butanol over Dowex 50Wx8-400. Chem. Eng.
33
34 13 J.l 2011, 168 (1), 293–302.
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36
37
14 [21] Charton, M. Steric Effects. 7. Additional V Constants. J. Org. Chem. 1976, 41 (12),
38
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40 15 2217–2220.
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42
43 16 [22] Kastratovic V. , Bigovic M., Esterification of Stearic Acid with lower Monohydroxylic
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45 17 Alcohols. 2017.
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48 18
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10 3 List of Figures:
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13 4 [1] Fig.1a.-1c. Effect of different initial mole ratio on esterification of acetic acid with n-
14
15 5 propanol, isopropanol and n-butanol respectively, at 353.15 K and 3% catalyst loading.
16
17
18 6 [2] Fig.2a.-2d. Effect of initial mole ratio on esterification of (a) formic acid at 343.15 K
19
20
21
7 and 3% catalyst loading, (b) propionic acid at 363.15 K and 5% catalyst loading, (c)
22
23 8 butyric acid at 373.15 K and 7% catalyst loading and (d) pentanoic acid at 383.15 K and
24
25 9 7% catalyst loading with n-propanol, isopropanol and n-butanol respectively.
26
27
28 10 [3] Fig. 3a.-3c. Effect of catalyst loading on esterification of acetic acid with n-propanol,
29
30
31
11 isopropanol and n-butanol respectively at 353.15 K and 1:4 mole ratio.
32
33
34 12 [4] Fig.4a.-4d. Effect of catalyst loading on esterification of (a) formic acid at 343.15 K
35
36 13 and 1:3 mole ratio of acid to alcohol, (b) propionic acid at 363.15 K and 1:4 mole ratio
37
38 14 of acid to alcohol, (c) butyric acid at 373.15 K and 1:4 mole ratio of acid to alcohol and
39
40
41
15 (d) pentanoic acid at 383.15 K and 1:6 mole ratio of acid to alcohol with with n-
42
43 16 propanol, isopropanol and n-butanol respectively.
44
45
46 17 [5] Fig.5a.-5c. Effect of temperature on esterification of acetic acid with n-propanol,
47
48 18 isopropanol and n-butanol respectively at 3% catalyst concentration and 1:4 mole ratio
49
50
51 19 of acid : alcohol.
52
53
54 20 [6] Fig. 6a, 6c and 6e, Linear plot of ― 𝐥𝐧 (𝟏 ― 𝑿𝑨) verses time in min. and fig. 6b, 6d
55
56 21 and 6f represents the linear plot of lnk vs 1/T resulting from the esterification of acetic
57
58
22 acid with n-propanol, isopropanol and n-butanol respectively.
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3 1 [7] Fig.7a.-7c. Effect of different carboxylic acids used in the esterification reaction with
4
5
6 2 n-propanol, isopropanol and n-butanol respectively at 343.15 K, 180 min. and 3%
7
8 3 catalyst loading.
9
10
11 4 [8] Fig.8a.-8c. Charton - correlation for sulphuric acid catalysed esterification between
12
13 5 n-propanol, isopropanol and n-butanol with series of acids (acetic, propionic, butyric
14
15
16 6 and pentanoic acid) respectively.
17
18
19 7 [9] Fig.9. Effect of length and branching of n-propanol, isopropanol and n-butanol with
20
21 8 acetic acid respectively on esterification reaction of acetic acid at 353.15 K.
22
23
24 9
25
26
27 10
28
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30
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34 12
35
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37 13
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20 8
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22 9
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35 15
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37 16
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39 17
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41 18
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44 19
45
46
47 20 Fig.1a.-1c. Effect of different initial mole ratio on esterification of acetic acid with n-
48
49 21 propanol, isopropanol and n-butanol respectively, at 353.15 K and 3% catalyst loading.
50
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52 22
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47 21
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50 22 Fig.2a.-2d. Effect of initial mole ratio on esterification of (a) formic acid at 343.15 K and
51
52 23 3% catalyst loading, (b) propionic acid at 363.15 K and 5% catalyst loading, (c) butyric
53
54
55
24 acid at 373.15 K and 7% catalyst loading and (d) pentanoic acid at 383.15 K and 7%
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