KINETICS OF THE LIQUID PHASE ESTERIFICATION

OF CARBOXYLIC ACIDS WITH ALCOHOLS IN THE

PRESENCE OF ACID CATALYSTS:
RE-INTERPRETATION OF PUBLISHED DATA

V R DHANUKA, V C MALSHE and S B CHANDALIAT

Department of Chemlcd Technology, Umverslty of Bombay, Mahmga, Bombay 19. India

(Received10 July 1975, accepted22 September1976)

Ahstraet-The data pubhshed on the kmeticcs of hqud phase esterdicatton of several carboxyhc acids with Merent
alcohols m the presence of sulphmz acid as a catalyst have been re-mterpreted on the basis of alkyl sulphunc acid
as a catalyst The emplrrcat equahons pubhshed m the hterature assume the reaction to be essenmlly ureverslble
and second order with respect to the acid and first order with respect to the alcohol By re-mterpretation, It IS
shown that the reaction could well be a reversible reaction. whch IS first order with respect to the acid and the
alcohol, respechvely. m the forward tie&on and 6rst order with respect to the ester and water, respectively, m
the reverse direction A few typical experunents were performed usmg butyl sulphunc acid as a catalyst for the
butanol-acetic acid system and the results obtamed coniirmed the basis of the re-mterpretatlon The predicted
conversions from the proposed rate equahon agree very well with those reported m the Meratare

The reaction between an alcohol and an acid to form an ceeds m two steps
ester and water IS of conslderable mdustrml unportance
‘Ilus reaction 1s usually camed out m the presence of a B+H,SO, - C+ W (102)
mmeral acid Sulphunc acid IS more commonly used
A+BAE+W (103)
because of Its superlonty over the other mmeral acids [ 11 CU¶&*t
The reaction may be represented by the followmg
equation where, C refers to alkyl sulphunc acid Experunents
have been camed out usmg A, B and C as the startmg
materials and it LS found that reaction (103) follows
A+B HzSo4as,E+ W (101)
can8lwt elementary reversible kmebcs

where A, B, E and W refer to carboxyhc acid, alcohol,

y=k, C&r1 KGVG
ester and water respectively Previous workers [ l-81 ( >
studled the kmetics of reaction (lOl), mostly m the
presence of excess alcohol and came up with a sug- where, k,, specdic reaction rate, l/mole hr, K, eqmhbrmm
gestion that the reaction may be second order with constant, CA, CB, CW, C,, concentrations of acid, alcohol,
respect to the acid water and ester respectively, mole/l
In tis paper, only the kmetics of reaction (103) for the
y = kc,= (0 sulphunc acid system has been studied It IS hoped that
after studymg the kmetics of reaction (102), one may find
where y, rate of reaction, mole/l hr, k, spectic reaction a proper overall rate equation for reaction (101) Further,
rate, 1 /mole hr, C,,, concentration of carboxyhc acid, after the uutm.l phase of the reaction, when sulphunc
mole/l acid IS completely converted to alkyl sulphmc acid, it
The specdic reaction rate “k” has been correlated w1t.h should be possible to reinterpret the pubhshed data by a
vmous process vanables by a complex empmcal equa- simple rate expression based on classical kinetics
tion
LIMITATIONS OF TEE -C! -0NS

1
PROPOSED BY THE PREYIOUS WORKERS
k= a+bW-c 2 W eVBIRT 00
(3 The expressions (1) and (n) were first proposed by
Leys and Othmer[l] and then adopted by almost all the
where a, 6, c, constants m eqn (u), C,, mtml concen- authors, who have stu&ed the esteticatton reacfion[2-
tration of the acid, mole/l , C,, nubal concentration of 7j However, the above expresslons have many llml-
the alcohol, mole/l , W, catalyst concentration, wt%, E, tations
energy of activation, k&/mole, R, gas constant, (1) The spec16c reaction rate is not an exphcit function
kcal/mole “K, T, temperature, OK of the concentration of the acid For the vmous alcohol
In this paper, It 1s proposed that reaction (101) pro- to acid ratios employed by them, it can be seen that for
almost the same alcohol concentration and the same
t’Zhe author to whom all commumcafions may be sent catalyst concentration, the value of specdic reaction rate

551
552 V R DHANUKA et al

vartes by a factor of 10 or more (Table 1) This IS difficult sulphunc acid as a catalyst would be considerably dfi-
to explam erent than that obtamed by usmg alkyl sulphunc acid as
(2) In view of the large excess of alcohol used, It 1s a catalyst It is also well known that the spectic reaction
possible to treat the reacuon as an essentially ureversible rate is strongly dependent on the catalyst concentration
reaction, without any slgticant error However, a more It is, therefore, expected that as the concentration of
general rate expression for the esterilication reaction sulphurlc acid depletes and the correspondmg alkyl
should take mto account the reversible nature of the sulphmc acid 1s formed, the specltic reaction rate would
reaction, so that the expression may be used even 111 decrease If this aspect IS not taken mto account and the
those cases, where the large excess of alcohol 1s not specific reaction rate 1s assumed to remam constant
employed during the progress of the reaction, the order of the
(3) Despite the fact that the specific reaction rate 1s reaction would appear more than one to account for the
not an explicit function of concentration, tins has been decrease 111the spectic reaction rate
used to determme the energy of activation
(4) In the case of the reaction catalysed by the cation EXPERIMENTS
WITE ALKYL. SULPEIJRIC ACID
exchange resms[9], the kmetic data are correlated by an AS A CATALYST

elementary reversible rate expresslon (eqn (m)) The In order to avoid the comphcations arising out of the
system employed here 1s the same as that employed by change of catalytic species durmg the course of reaction.
Leys and Othmer[l] It would be surprismg to find that It was considered desvable to start with alkyl sulphuIlc
the esteniicatlon of butanol with acetic acid 1s second acid alone as a catalyst Thus was done by reactmg the
order with respect to the acid m the presence of sul- usual amount of sulphunc acid and the alcohol for
phunc acid as a catalyst, when the same reaction 1s iirst suBiclent tnne so that the entie amount of sulphurlc acid
order with respect to the acid, when cation exchange IS converted to alkyl sulphmc acid, before the car-
resm IS used as a catalyst It may also be added that m boxyhc acid 1s added for conductmg the estetication
the absence of a catalyst, the estenficatlon reaction 1s reaction under consideration The acldlmetrrc titration
known to be first order with respect to the acld[lO] and it confirmed that the sulphunc acid was completely con-
follows eqn (m) The ester&cation of acetic acid and verted to alkyl sulphurlc acid Under the condltlons
ethanol with hydrochloric acid as a catalystlll] also employed, It does not undergo further reachon to dl-alkyl
follows eqn (m) sulphate Thus was ascertamed by contuuung the reaction
In view of the foregomg, it was thought desirable to for 2 more hr, when no change m the acid value was
re-interpret the published data observed
In order to examme whether the alkyl sulphurlc acid
TEF, COMPLICATIONS DUE TO THE CEANGE IN formed m the reaction system does not hydrolyse back
TEE CATALYTIC SPECIES to alcohol and sulphurlc acid under the reaction con-
It IS well known that sulphunc acrd undergoes reaction dltlons, an experiment was conducted with sulphurlc acid
with alcohol to form mono-alkyl sulphurlc acid and butanol for 2 hr at lOO”C, to form the alkyl sulphurlc
acid, and then water, correspondmg to the amount that
R’-OH + H,SOA + R’-O-S03H + Hz0 (102) would usually be formed by the esterticatlon reaction,
B C was added and the reaction was contmued for 1 hr at
100°C It was found that the butyl sulphurrc acid once
Under the conditions employed a very large excess of formed did not hydrolyse back to sulphunc acid, under the
alcohol 1s present and therefore, the reaction tends to reactlon comhtions In view of tbs, It 1s possible to conduct
be essentially ureverslble Most of the mves@ators have an esteticationreactlon usmg alkyl sulphurlc acid alone as
carried out thy reaction m the absence of carboxyhc acid a catalyst
to account for the sulphmc acid and mono-alkyl sul-
phurlc acid, because they follow the kmetlcs of the EXPERIMENTAL

estetication reaction by acldlmetric analysis However, The system butanol-acetlc acid, which has been em-
they have not taken mto consideration the phenomenon ployed by Leys and Othmer[l] was selected for m-
of conversion of sulphurrc acid to mono-alkyl sulphunc ves@ation The experiments were conducted by first
acid, wMe consldermg the concentration of catalyst in reacting butanol with sulphurlc acid for 2 hr at 100°C so
the kmetlc mterpretation The specific reaction rate with that the complete conversion of sulphurlc acid to butyl
sulphunc acid IS ensured, and then takmg tis mixture
Table 1 Experimental values of specdic reactlon rate as re- and acetic acid m sealed tubes The ester&cation reac-
ported by Leys and Othmer[i] usmg sulphunc acid as a catalyst tlon was conducted by lmmersmg the sealed tubes m a
constant temperature bath mamtamed at 100°C The
Sr C, Cm CEb Catalyst k
No (mole/l ) (mole/l ) CA, cone (wt%) (1 /mole hr) reactlon was followed by removing the tubes at different
time mtervals, ch&ng these m Ice- vater mixture and
1 3 10 9 033 2991 0069 0 01986 then analysmg the contents by acldunetrlc analysis
2 194 9 707 4992 0 0679 004115
3 1 025 10 286 10 030 00711 0 09327 RESULTSAND DISCUSSION
4 0 539 10 5928 19 620 0 0692 0 23180
V~IXOUSpossible reaction models were conssdered and
System Butanol-acetlc acid It was found that the data could be correlated most
 Kmetlcs of the llquld phase estenlicahon of carboxyhc acids 553

satlsfactordy by eqn (m) This suggests that the kmetlcs show a considerable vartatton In the absence of a con-
of esteficatlon m the presence of sulphunc acid as a stant value for eqmhbrmm constant, the specdic reaction
catalyst appears to be comphcated only because the rates were calculated by assuming vmous values of
previous mvesmators have not consldered the change m eqmhbnum constant between the reported range The
the catalyst species, which takes place durmg the course spectic reaction rates were further correlated with
of the reactlon If alkyl sulphurlc acid alone 1s used as a catalyst concentration by eqn (iv) by hnear least square
catalyst, as m the above experiments, the specific reac- method Even though there 1s some uncertamty regardmg
tion rate remams essentially constant when the data are the value of K, It was found that when dfierent values of
correlated by eqn (m), which confirms the vahdlty of the K as reported m the literature were used, the change m
equation (Table 2) the values of a and p obtamed was margmal (Table 3)
The values of the specific reaction rate at various This IS understandable because m the presence of a large
catalyst concentrations can be correlated w&h the ca- excess of alcohol, the reverse reaction 1s nemble as
talyst concentration C,, by the followmg equation compared to the forward reaction and therefore, even a
large inaccuracy m the value of K would not cause any
k, = a + PC, w sign&ant error m the determination of the specdic
reaction rate In order to select one typlcal value of K,
where, a 1s the spectic reactlon rate for non-catalytic the highest reported value was arbltrardy chosen Based
reaction, and /3 IS a constant The value of a was on the values of a and #3 obtamed, the x vs t data were
calculated from the results reported by Leys and regenerated and were transferred back to zero tune A
Othmer [ I] and based on the mean value of a, the value plot of experimental conversion versus calculated con-
of p was calculated version for the various systems considered shows that
the proposed equations predict the expenmental data
REINTERPRETATION OF THE RESULTS REPORTED satlsfactordy (Figs l-4) The value of a and /3 as
IN THE LITJ!XATuRE calculated from the re-mterpretation of the data of Leys
The kmetlc data reported by Leys and Othmer [l] on and Othmer [l] 1s m very good agreement with that
the esterrfication of n-butyl alcohol and acetic acid and obtamed experlmentally m this work, when alkyl sul-
those by Hussam and Kamath[4] on the ester&cation of phurlc acid alone was used as a catalyst (sac = 0 00591,
methanol with benzolc acid, sahcyhc acid and aexpt = 0 00644, varMion = 24 2%, /Seal== 30 19, &XPt =
monomethyl phthalate, respectively, were considered for 31 72, varlatlon = 22 5%)
re-mterpretation It 1s reported by these mvestlgators
that sulphurlc acid 1s completely converted to aIkyl- BTERIFICATION M TEDI PRESFJKE OF
sulphunc acid m less than 30 mm Therefore, the OTEER ACID CATALYSTS
concentrations of the alcohol, the acid. the ester and When esteticatlon 1s camed out m the presence
water reported at 30 mm were taken as uutml concen- of acids other than sulphmc acid, such as hydrochlonc
tration and the conversions based on the above lmtlal acid, p-toluene sulphomc acid, perchlonc acid, etc the
concentration of the acid were employed for the kmetic acid correspondmg to alkyl sulphunc acid 1s not formed
mterpretatlon This would amount to esterlficatlon m the Under the conditions employed, alkyl chloride IS unhkely
presence of alkyl sulphurlc acrd alone as a catalyst and, to be formed by the reaction of alcohol and hydrochlonc
therefore, the comphcatlons arlsmg m the kmetic mter- acid Slmdarly it 1s unhkely that perchlorlc acid and
pretatlon of the previous workers would be ellmmated p-toluene sulphomc acid would react with alcohol
The calculations were performed on a CDC-3600 Therefore, the kmetrcs of esterScation m the presence
computer The values of equlllbrmm constant, K, are of these catalysts should follow the eqn (m) and no
avadable m the literature However, the reported values comphcatlon should arise m the kmetlc mterpretation

Table 2 Results of kmetlc runs usmg alkyl sulphunc acid as a catalyst

Run C, C,x 10” Molar t Mean Std dew Mean

No (mole/l ) (mole/l ) ratio (hr) 05 10 I 5 20 30 40 50 (k, x 102) (k, x 102) #3

1 0 9021 7377 105 x 01124 02510 03533 04259 05117” 05673” - - - -

k,x 1W 2539 3 102 3 1410 3 0170 3 144 3 036 - 3005 02157 3195

2 0 9359 7248 1005 x 01335 02520 03427 04242 OS334 06223 06908 - - -

k,xlff 3062 3 126 3 032 3 011 2804 2 719 2 656 2 919 0 1182 31 32

3 14788 14 213 615 X 019935 03859 04928 05822 06891 - - - - -

k,XlW 4993 5 602 5 29 5 197 4 789 - - 5 174 05277 3188

mean=3172

“t=25hr
*t=3ohr
System Butanol-ace& acid Temperature = IWC, K = 2 87, a = 6 44 x low3
 554 V R DHANUKA et al

Table 3 Calculated vaIues of specdic reaction rate for non-catalytic reactron (Q)
and constant (/3) m eqn (IV) for various systems

MonomethyP
Acetic acld” Benzo~c acldb Sshcyhc acldb phthalate
System + Butanol + Methanol + Methanol + Methanol

K 2 7’ 287 098 178 0575 186 0 49 1 105

CrXlF 3 18 591 742 753 207 2 14 3 81 4 01
B 32 55 30 19 00683 005% 0 00906 000855 0 0159 00141

“Data of Leys and Othmer[l]

*Data of Hussam and Kamath[4]
‘For value of K < 2 7 the log function m the mtegrated expresslon becomes
negative

06
_s

E05

;04
P
z03

01 02 03 04 05 06 07 08 09 IO
Experimental c*nverson Experimental conversion

Flp 1 Experunental vs predlcted converslon for the system Fig 3 Experunental vs prehcted conversion for the system
acehc acid-butanol [ 11 sahcyhc acid-methanol[4]

IO

09

06

01 02 03 04 05 06 07 06 OS IO
oov 0 01
n
02 03 04 05 06 07 06 c
Expetwnental convers~o” Experimental conversion

Fag 2 Expenmental vs predicted converslon for the system Fig 4 Expenmental vs predhcted converslon for the system
benzolc acid-methanol [4] mono-methyl phthalate-methanol[4]

The lonetic data on the ester&cation of sahcyhc acid DISCDSSION AND CONCLUSIONS
with methanol are reported by Hussam[8], though these hqmd phase esterdkation
(I) The of an acid with an
have not been mterpreted by the author It IS found alcohol m the presence of catalysts such as hydrochloric
(Table 4) that these data can be satisfactorily correlated acid, perchlorlc acid or p-toluene sulphoruc acad follows
by eqn (m) elementary reversible kmetics
Kmetlcs of the hquld phase esterdicatlon of carboxyhc acids 555

(II) When sulphunc acid IS used as a catalyst [reaction

(lOl)] there IS a comphcatlon because sulphmc acid
undergoes a reaction with the alcohol to form alkyl
sulphurlc acid [reactlon (102)l
(m) The esterlficatlon m the presence of alkyl sul-
phurlc acid alone as a catalyst [reaction (103)] follows
elementary reversible kmetlcs
(m) The fit of eqn (al) for the reaction (103) m ths
work and the fit of eqn (II) for the reaction (101) as
reported by the previous workers are lust about equally
good
(v) If the reaction 1s carried out m the usual manner,
where one starts with carboxyhc acid, alcohol and sul-
phmc acid, the simple expression proposed m this work
would not fit well m the early stages of the reactlon and
the empulcal expression proposed by Othmer (eqn (u))
would be more suitable In this work, the kmetics of only
reaction (103) has been studied If the kinetics of reac-
tion (102) 1s also studied, it may be possible to find a
proper overall rate equation for reactlon (101)
(VL) If alcohol 1s allowed to react with sulphunc acid
for a sufficient time so that the alkyl sulphurlc acid IS
formed before the carboxyhc acid 1s added to carry out
the esterdicatlon reaction, it would amount to reaction
(103) and the data could be correlated by an elementary
reversible rate expression, which 1s simple and based on
classical kmefics
NOTATION
a, b, c empulcal constants m eqn (n)
CA concentration of the acid, mole/l
CB concentration of the alcohol, mole/l
CC concentration of the catalyst, mole/l
CB concentration of the ester, mole/l
cw concentration of water, mole/l
Go nutlal concentration of the acid, mole/l
GO uutlal concentration of the alcohol, mole/l
E activation energy, kcal/mole
k, k, specfic reaction rate, 1 /mole hr
K eqmhbrmm constant
R gas constant, kcallmole “K
t time, hr
T temperature, “K
W weight of the catalyst, g/lOOg reaction mixture
x fractional conversion

Greek symbols
a non-catalytic rate constant, 1 /mole hr
fi constant in eqn (v), 1 ‘/mole’ hr
y rate of reaction, mole/l hr

REFERENCES
[l] Leys C E and Othmer D F , Znd Engng Chem 1945 37
%8
[2] Berman S , Melnchuk A A and Othmer D F , Znd Engng
Chem 1948 40 1312
[3] Reddy G S and Hussatn S Z , Znd Chem Engrs Trnns
1%7 9 31
[4] Hussam S Z and Kamath N R , Znd J Technol 1%7 5 92,
1%7 5 179
[5] Agarwal S C , Nageshwar G D and Mene P S , Znd Chem
Engrs Trans 1%9 It 93
[ti] McCracken D J and Dickson P F , Znd Engng Cfiem
Proc Des Develop 1%7 6 286
556 V R DHANUKA et al

[7] Hussam S Z and Kamath N R , Bnt Chem Engng I%8 13
957
[8] Hussam S Z , Ph D Thesis. I IT Bombay (1967)
[9] Kekre S Y and Gopala Rao M , Ind Chem Engrs Truns
1%9 11 115
[lo] Rosanoff M A and Prager W L , J Am Chem Sot 1908
30 1895, 1908 30 1908
[ll] Smith J M , Chem~ol Engmeermg Kmetrcs. 2nd Edn, pp
91, 314 McGraw Hdl, New York 1970