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Kinetics of Oxidation of Benzyl Alcohol with Dilute Nitric Acid
Sudhir R. Joshi, Kamal L. Kataria, Sudhirprakash B. Sawant,* andJyeshtharaj B. Joshi
 Institute of Chemical Technology, University of Mumbai, Matunga, Mumbai 400 019, India
The oxidation of benzyl alcohol by dilute nitric acid has been selected for the study as a typicalmethod for the manufacture of industrially important intermediate benzaldehyde. All thereactions have been performed in the absence of any solvent. A catalytic amount of sodium nitriteis essential for the generation of active state of nitrogen. Benzyl nitrite is formed in a substantialamount as an intermediate. The effects of various parameters such as the NaNO
2
loading, nitricacid concentration, temperature, and molar ratio have been investigated. The stoichiometricrequirement of nitric acid for benzyl alcohol conversion has also been determined. The probablemechanism for the oxidation of benzyl alcohol using nitric acid is proposed, showing the reversibleformation of benzyl nitrite and its irreversible decomposition to benzaldehyde. The mass-transferresistance has been eliminated for the investigation of kinetics of all the reactions in theconsecutive path. The influence of chloro substitution on the oxidation rates of 2-chlorobenzyl,4-chlorobenzyl, and 2,4-dichlorobenzyl alcohols has been presented.
1. Introduction
Benzaldehyde (BzH) and substituted benzaldehydesare important perfumery and pharmaceutical interme-diates. Benzaldehyde is a starting material for odorantsand flavors. Substituted benzaldehydes are used in themanufacture of pharmaceuticals (e.g., 2-chlorobenz-aldehyde is used in the manufacture of amlodipin, cloxa-cillin, and clobenzorex; 4-chlorobenzaldehyde is used inthe manufacture of baclofen, chlormezanone, chloro-pyramine; and 2,4-dichlorobenzaldehyde is used in themanufacture of halofantrine
1
).The conventional routes for the synthesis of BzHinclude hydrolysis of the benzal chloride and the vapor/ liquid-phase oxidation of toluene. With the formerprocess, it is impractical to obtain the chlorine-freeBzH.
2
Furthermore, the chlorination reaction operatesat lower conversion levels, requiring a large recyclingof recovered toluene. The vapor-phase catalytic oxida-tion of toluene results in a loss of carbon in the form of carbon oxides, in addition to lower conversion (10%
-
20%) and poor selectivity (30%
-
50%). Although theliquid-phase oxidation of toluene prevents the carbonloss, it requires a homogeneous catalyst (such as cobalt,25
-
1000 ppm), high pressure (2
-
70 kg/cm
2
), and hightemperature (136
-
160 °C).
2
 Also, the BzH that isproduced is further oxidized, because it has a loweractivation energy than its heat of formation, resultingin poor selectivity.
3
These factors make the processtechnically and economically unattractive.Benzyl alcohols are attractive raw materials for themanufacture of BzHs. The oxidation of benzyl andsubstituted benzyl alcohols to corresponding aldehydeshas been investigated over the past forty years, withincreased focus during the past twenty years. Severaloxidants, such as permanganates,
4,5
dichromates,
6,7
hypohalides,
8,9
peroxides,
10,11
and molecular oxygen
12
-
14
with or without phase-transfer catalysts (PTCs) andheterogeneous catalysts have been used successfully forthe oxidation of benzyl alcohol to BzH. The catalyticoxidation of benzyl alcohol using molecular oxygenrequires a heterogeneous catalyst, high temperature(210 °C), and longer reaction times (
>
5 h). Although thereported selectivity is quite good (75%
-
95%), the con- version levels are too low (maximum of 40%).
14
Practically, in all the previously cited cases, goodyields have been obtained, with respect to BzH; how-ever, the conversion levels were lower and/or not beenreported in many cases. Furthermore, the inorganicoxidants (along with PTC reagents and their amounts)seem to be cost prohibitive for the large-scale com-mercial production of aldehydes. In this respect, nitricacid is known to be a favorable oxidizing agent.
15,16
Thepublished literature on the HNO
3
-based oxidation of alcohols to aldehydes/ketones has been summarized inTable 1. The oxidation of benzyl alcohols to BzHs bydilute nitric acid (
∼
10%) in the presence of a catalyticamount of NaNO
2
, in 40 vol % dioxan as a solvent, wasfirst studied in detail by Ogata et al.
15
They proposedthat the reaction proceeded through some intermediate;however, it was not identified. Many other investigatorshave also studied the oxidation of benzyl alcohol usingnitric acid.
17
-
21
However, the published informationsuffers from two limitations: (i) oxidation studies havenot been performed in the absence of solvent, to makethe process commercially more attractive, and (ii) thekinetics of oxidation reaction have not been reported.Due consideration to the formation of benzyl nitrite asan intermediate is needed. The kinetic parameters alsomust be free from any mass-transfer limitations. Theseissues have been addressed in the present work.Thus, benzyl alcohol was reacted with nitric acid inthe presence of a catalytic amount of sodium nitritewithout any solvent. The oxidation system has beenapplied for the synthesis of chloro benzaldehydes fromcorresponding chloro benzyl alcohols as well.
2. Experimental Section2.1. Method.
All the experiments were conducted ina batch manner. A borosilicate glass reactor with aninner diameter (id) of 75 mm and capacity of 400 mL,which was equipped with a pitched-blade downflow
* To whom correspondence should be addressed. Phone: 91-22-2414 5616. Fax: 91-22-2414 5614. E-mail: sbs@udct.org.
325
 Ind. Eng. Chem. Res.
2005,
44,
325
-
333
10.1021/ie0303911 CCC: $30.25 © 2005 American Chemical SocietyPublished on Web 12/14/2004
 
turbine impeller (25 mm in diameter) and baffle, wasused. The reaction temperature was maintained usinga constant-temperature bath. A predetermined quantity of benzyl alcohol was addedto the reactor. A measured quantity of sodium nitritewas then added, followed by the addition of aqueousnitric acid that was preheated to the required temper-ature; the run then was started. Extremely low solubil-ity (4 wt %) of the benzyl alcohol in aqueous nitric acidmakes the system have two phases (organic and aque-ous). Small quantities of samples of the two-phasemixture were withdrawn at predetermined time inter- vals. After the sample was withdrawn, it was quicklyadded to water. As a result, the dissolved nitric acid inthe organic phase was extracted back into the aqueousphase and the reaction became quenched. The organicphase (which was separated from the water phase) wasused for further analysis. The sample was divided intotwo parts. The first part was analyzed via gas chroma-tography(GC),toestimatetheamountsofbenzylnitrite,benzaldehyde that had formed, and unconsumed benzylalcohol. The second part of the sample was analyzed viathin-layer chromatography (TLC), using a Dessaggaapplicator and scanner to determine the amount of benzoic acid (BzOH) formed.
2.2. Analysis.
The various species that participatein the reaction, and their probable paths, can be shownas follows:BnOH, BnONO, and BzH were analyzed via GC. TheGC analysis was performed using a 2-m 10% OV-17column. Nitrogen was the carrier gas, and the detectorwas a flame ionization detector. The other parameterswere as follows: injection temperature, 350 °C; detectortemperature, 350 °C; nitrogen flow rate, 30 mL/min; andtemperature programming, 110 °C (isothermal).For the analysis of BzOH via TLC, precoated silicagel plates (Merck) were used. A portion (0.2 mL) of thesample was diluted to 10 mL with acetone. Knownquantities of the diluted sample and the authenticsample of BzOH were applied in the form of 5-mmbands, using the applicator (Dessagga). The plates weredeveloped in a solvent system that consisted of benzeneand methanol (5:1, by volume). A densitometer (Des-sagga) was used to analyze the developed plates.
3. Theory of Mass Transfer with ChemicalReaction
In order to estimate the true kinetic parameters, weneed to (i) eliminate the mass-transfer resistances, (ii)know the phase in which the reactions occur, and (iii)according to the classification ofheterogeneousreactionsgiven by Doraiswamy and Sharma,
22
establish thereaction regime for the present case.To begin, the following reaction mechanism is pro-posed; the supporting observations will be explainedlater.
3.1. Reaction Mechanism.
The overall reaction is given byThe oxidation reaction of BnOH by dilute nitric acidproceeds via benzyl nitrite (BnONO). HNO
2
is formedby the reaction of NaNO
2
and HNO
3
. The HNO
2
is thetrue oxidant and reacts with alcohol to give nitrite esterand, thus, the reaction is initiated. The nitrite esterdecomposes in an acidic medium to give aldehyde andHNO or reversibly yielding BnOH back. The excessHNO
3
oxidizes HNO to HNO
2
and the oxidation cyclecontinues. Thus, as the reaction proceeds, HNO
3
isconsumed. HNO finally undergoes self-decomposition togive nitrous oxide and water.
Table 1. Reported Oxidation of Benzyl Alcohols by Nitric Acid and Nitrous Acid
author oxidation system solvent resultsGray et al.
18
H
2
SO
4
+
excess NaNO
2
no solvent (1) formation of BnONO as an intermediate;(2) decomposition of BnONO to BnOH and BzH; and(3) 1st order decomposition with
E
)
154.81 kJ/mol and anF-factor of 10
13
s
-
1
Ogata et al.
15
HNO
3
(20%)
+
NaNO
2
40% dioxan (1) NaNO
2
is needed for the reaction to proceed;(2) minimum acidity of 0.1 M is necessary for the oxidation;(3) first-order dependency on nitric acid and BnOH;(4)
E
)
117.28 kJ/mol; and(5) substitution effect was shown to satisfy Hammett’sequation, with a slope of 
-
2.5Ross et al.
16
HNO
2
+
HNO
3
in H
2
SO
4
(50%
-
70%) by NaNO
2
no solvent (1) nitrosonium is an active oxidant;(2)
E
)
44.35 kJ/mol; and(3) substitution effect is shown to follow Hammett’s equation,with a slope of 
-
1.4Gasparrini et al.
20
20% HNO
3
nitromethane (1) good yields (95%) of aldehyde;(2) various substitutions with
+
σ 
and
-
σ 
have been shownto be oxidized by this systemNishiguchi and Okamoto
21
NO
2
in presence of silica gel no solvent (1) oxidation of alcohols and ethers to aldehydes and ketones;(2) alky/aryl nitrite used as an intermediate;(3) NO
2
in radical form as an active species; and(4) NO
2
also accelerates the decomposition of the formednitrite intermediate to aldehyde/ketoneLevina and Trusov
19
O
2
+
HNO
2
in conc. HClO
4
,H
2
SO
4
, F
3
CCOOHno solvent (1) oxidation of BnOH and various other primary andsecondary alcohols; and(2) NO
+
used as an active species for the reaction
BnOH
f
BnONO
f
BzH
f
BzOH (1)2R
-
CH
2
OH
+
HNO
3
f
2R
-
CHO
+
12N
2
O
+
52H
2
O(7)
326
Ind. Eng. Chem. Res., Vol. 44, No. 2, 2005
 
Table 2 shows that the ratio of alcohol consumed toHNO
3
at different reaction conditions is
∼
2.0. This isconsistentwiththestoichiometricrequirementindicatedby eq 7. In addition, the gas-phase analysis (Suchak etal., 1989) was performed in an operating plant, usingthe HNO
3
oxidation of benzyl alcohol. It was observedthat the gas phase did not contain NO, NO
2
, N
2
O
4
, orN
2
O
5
. Thus, it may be concluded that the NO
 x
that isliberated is in the form of N
2
O. The liberated N
2
O inthe product gas mixture can be used as a clean andselective oxidant, e.g., for the selective oxidative cou-pling of methane to ethane (Sugiyama et al.
23
) and forthe oxidation of benzene to phenol (Reitzmann et al.
24
).
3.2. Identification of the Phase in Which Reac-tionOccurs.
Benzyl alcohol oxidation by aqueous nitricacid is a typical example of consecutive liquid
-
liquidheterogeneous reaction. The reactant benzyl alcohol andthe reaction products form the organic phase, while thedilute nitric acid forms the aqueous phase. The reactionproceeds through the formation of a benzyl nitriteintermediate, as discussed previously. The formation of benzyl nitrite by the reaction between benzyl alcoholand in-situ-generated nitrous acid may be consideredto be similar to the well-known nitration reaction, whichoccurs in the aqueous phase (see Zaldivar et al.
25
andD’Angelo et al.
26
). Also, in the present case, for a fixednitric acid concentration, an increase in the volume of the aqueous phase gave a proportionate increase in therate of reaction (given in kilomoles per second, kmol/s)and the volumetric rate of reaction (given in kilomolesper cubic meter of aqueous phase per second, kmol m
-
3
s
-
1
) remained the same. The relative amount of organicphase did not have any effect on the volumetric rate of reaction. These evidences indicate that the rate-limitingstep of the reaction occurs in the aqueous phase.
3.3. Identification of Reaction Regime.
Let uswrite eq 7 in the following form:where A and B are the benzyl alcohol and nitric acid,respectively, and
z
is a stoichiometric coefficient (in thepresent case,
z
)
0.5). Because the reaction occurs inthe liquid phase, the overall oxidation follows these twosteps: (i) mass transfer of benzyl alcohol to the aqueousphase and (ii) the reaction between the dissolved benzylalcohol (A*) and nitric acid (B
0
). The details that pertainto heterogeneous reactions (consisting of the steps of mass transfer and chemical reaction) have been givenby Danckwerts
27
and Doraiswamy and Sharma.
22
Theyclassified these reactions into four regimes, dependingon the rates of mass transfer, relative to the rates of chemical reaction in other words, when the rate of chemical reaction is very much slower than the rate of mass transfer, or when the condition given by thefollowing expression is satisfied:where
m
and
n
are the orders, with respect to benzylalcohol and nitric acid, respectively, and
L
is the volumetric fraction of the aqueous phase. Under theseconditions, the overall reaction is controlled by thechemical reaction (regime 1) and the volumetric rate of reaction is given by the following equation:When the reverse condition given by expression 8 issatisfied, or if the rate of reaction is faster than the rateof mass transfer, the overall rate is controlled by masstransfer (regime 2) and is given byWhen the reaction rate increases further, the reactionoccurs in a region close to the interface and is completedin the film. The necessary condition for this phenom-enon is as follows:For reaction regimes 1 and 2 (determined by eqs 9 and10), the value of 
 
 M 
(the Hatta number) must be
<
1,preferentially 0.1.
3.4. Effect of Impeller Speed.
Since, in a liquid
-
liquid system, the values of 
k
L
and
a
are dependent onthe impeller speed, it was believed to be desirable toinvestigate the effect of impeller speed. For this purpose,0.3 mol BnOH was reacted with 118 mL of 1.59 Maqueous nitric acid in the presence of 1 g of NaNO
2
at90 °C. The reaction was performed at stirring speeds of 25 and 41.66 rps. Figure 1A shows the conversion of BnOH with time. Variation in the yields of the products
s
aldehyde, acid, and nitrite
s
at two speeds is shown inpanels B, C, and D, respectively, of Figure 1. The resultsshow that the reaction is not affected by stirring speedsbeyond 25 rps, the rate is not dependent on
k
L
and
a
,or the reaction is kinetically controlled when the speedexceeds 25 rps. However, as an abundant precaution,all the experiments in the present work have beenconducted at an impeller speed of 41.66 rps, to ensurethat the reaction proceeds under a kinetically controlledregime and the true kinetic parameter can be evaluated.For confirmation, it was thought desirable to estimatethe values of 
 
 M 
in eq 11. For this purpose, correla-tions that were proposed by Keey and Glen
28
and VanHeuven and Beek
29
were used for the estimation of the
k
L
, and the diffusivity was estimated using the proce-dure that was proposed by Garne and Merchant.
30
Tables 3 and 4 give the values of 
 
 M 
under the rangeof experimental conditions covered in this work. It canbe seen that the values of 
 
 M 
are
<
0.04. The foregoingevidence clearly indicates that the oxidation reaction
Table 2. Consumption of Nitric Acid for Oxidation of Benzyl Alcohol
a
yield (%)BnOH:HNO
3
molar ratiotemperature(°C)batch time(min)conversion of benzyl alcohol(%) BzH BnOH BnONOHNO
3
consumed(mol)ratio of consumed alcoholto HNO
3
1:0.625 70 240 73.18 85.45 1.82 12.73 0.106 2.071:0.625 80 240 82.98 94.84 3.5 1.65 0.12 2.071:0.625 90 240 86.74 95.11 4.54 0.35 0.148 1.761:1.25 70 230 91.90 92.31 2.89 4.80 0.131 2.10
a
BnOH content
)
0.3 mol, HNO
3
concentration
)
1.59 M, NaNO
2
content
)
1 g, and speed of stirring
)
41.66 rps.
 A
+
 z
B
f
products
k
L
a
[A*]
.
L
k
mn
[A*]
m
[B
o
]
n
(8)
 R
)
L
k
mn
[A*]
m
[B
0
]
n
(9)
 R
)
k
L
[A*] (10)
 
 M 
)
 
[2/(
m
+
1)]
 D
 A
k
mn
[A*]
m
-
1
[B
0
]
n
k
L
>
3 (11)
Ind. Eng. Chem. Res., Vol. 44, No. 2, 2005
327
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