Article No : a18_247

Oxalic Acid
WILHELM RIEMENSCHNEIDER RETIRED, Hoechst AG, Frankfurt, Federal Republic
of Germany
MINORU TANIFUJI, Ube Industries, Tokyo, Japan

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . 529 6.2. Textile Treatment . . . . . . . . . . . . . . . . . . . . 537

2. Physical Properties . . . . . . . . . . . . . . . . . . . 530 6.3. Bleaching Agents . . . . . . . . . . . . . . . . . . . . . 537
2.1. Anhydrous Oxalic Acid . . . . . . . . . . . . . . . . 530 6.4. Chemical Uses . . . . . . . . . . . . . . . . . . . . . . . 538
2.2. Oxalic Acid Dihydrate . . . . . . . . . . . . . . . . . 530 7. Economic Aspects . . . . . . . . . . . . . . . . . . . . 538
3. Chemical Properties . . . . . . . . . . . . . . . . . . 531 8. Storage, Handling, Transportation, Waste
4. Production Processes and Raw Materials . . 531 Disposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538
4.1. Oxidation of Carbohydrates . . . . . . . . . . . . 532 9. Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . 538
4.2. Oxidation of Ethylene Glycol. . . . . . . . . . . . 533 9.1. Salts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538
4.3. Oxidation of Propene. . . . . . . . . . . . . . . . . . 534 9.2. Organic Derivatives . . . . . . . . . . . . . . . . . . 539
4.4. Production from Carbon Monoxide . . . . . . 535 10. Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . 540
4.5. Production of Anhydrous Oxalic Acid . . . . . 536 References . . . . . . . . . . . . . . . . . . . . . . . . . . 541
5. Chemical Analysis . . . . . . . . . . . . . . . . . . . . 536
6. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 537
6.1. Metal Treatment . . . . . . . . . . . . . . . . . . . . . 537

1. Introduction Spinach 460 – 3200

Rhubarb 500 – 2400
Oxalic acid, ethanedioic acid, acidum oxalicum, Chard 690
has the structural formula Parsley 190
Beets 340
Cocoa 4500
Tea 3700
Beet leaves up to 12 000

and is the simplest saturated dicarboxylic acid
[1]. The compound exists in anhydrous form
[144-62-7] or as a dihydrate [6153-56-6]. The
anhydrous acid is not found in nature and must be
prepared from the dihydrate even when produced
industrially. Oxalic acid is widely distributed in
the plant and animal kingdom (nearly always in
the form of its salts) and has various industrial
applications.
The acidic potassium salt of oxalic acid is
found in common sorrel (Latin: oxalis acetosella)
and the name oxalic acid is derived from that
plant. Examples of plants in which oxalic acid
occurs (in the form of potassium, sodium, calci-
um, magnesium salts, or iron complex salts) are
given below (oxalic acid content in milligrams
per 100 g dry weight):
Oxalic acid is formed in plants through in-
complete oxidation of carbohydrates, e.g., by
fungi (Aspergillus niger) or bacteria (acetobac-
ter) and in the animal kingdom through carbohy-
drate metabolism via the tricarboxylic acid cycle.
The urine of humans and of most mammals also
contains a small amount of calcium oxalate. In
pathological cases, an increased calcium oxalate
content in urine leads to the formation of kidney
stones [2]. Calcium and iron(II) oxalates are also
found as minerals.
Oxalic acid is one of the oldest known acids
and was already identified in the potassium salt of
sorrel by WIEGLEB in 1769. The compound also
has historical significance in chemistry because
WOEHLER prepared oxalic acid by hydrolysis of
cyanogen [460-19-5] in 1824, thereby synthesiz-

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

DOI: 10.1002/14356007.a18_247.pub2
530 Oxalic Acid Vol. 25

1 1
Thermal conductivity (0 C) 0.9 W m K
ing the first natural product, even before his Ionization constant
famous urea synthesis in 1828. K1 6.5102
K2 6.0105

2. Physical Properties
2.2. Oxalic Acid Dihydrate
Both the anhydrous and dihydrated forms of
oxalic acid form colorless and odorless crystals. Oxalic acid dihydrate [6153-56-6],
HOOCCOOH  2 H2O is the industrially pro-
duced and usual commercial form of oxalic acid.
2.1. Anhydrous Oxalic Acid The compound forms colorless and odorless
prisms or granules that contain 71.42 wt % oxalic
Anhydrous oxalic acid [144-62-7] exists as acid and 28.58 wt % water. Oxalic acid dihydrate
rhombic crystals in the a-form and as monoclinic is stable at room temperature and under normal
crystals in the b-form [3]. These forms differ storage conditions. The most important physical
mainly in their melting points. The slightly stable properties are as follows:
b-form changes into the a-form at 97
C and
0.2 bar. Anhydrous oxalic acid is prepared by Mr 126.07
dehydration of the dihydrate through careful mp 101.5
C
heating to 100
C. It is then sublimated in a dry Density d420 1.653 g/cm3
air stream. The sublimation is fast at 125
C and Refractive index n20
4 1.475
Standard enthalpy of formation 1422 kJ/mol
can be carried out at temperatures up to 157
C DH
f (18
C)
without decomposition. The dehydration can Enthalpy of solution (in water) 35.5 kJ/mol
also be accomplished by azeotropic distillation pH (0.1 M solution) 1.3
with benzene or toluene [4]. Anhydrous oxalic Water vapor partial pressure
at 20
C 2.5 kPa
acid is slightly hygroscopic, it absorbs water at 50
C 20 kPa
from moist air (‘‘weathers’’) to form the dihy- Bulk density, regular product 0.977 g/cm3
drate again. The hydration occurs very slowly Bulk density, coarse product 0.881 g/cm3
because of surface caking. The physical and
thermal chemical properties of anhydrous oxalic
The solubility in water and the density of these
acid may be summarized as follows:
solutions are presented in Table 1 [5]. Oxalic acid
is readily soluble in polar solvents such as alco-
hols (although partial esterification occurs), ace-
Mr 90.04 tone, dioxane, tetrahydrofuran, and furfural.
mp Oxalic acid is sparingly soluble in diethyl ether
a 189.5
C
b 182
C
(1.5 g oxalic acid dihydrate in 100 g ether at
Decomposition temperature 187
C 25
C), and insoluble in benzene, chloroform,
Density d420
a 1.900 g/cm3 Table 1. Solubility of oxalic acid in water at different temperatures
b 1.895 g/cm3 and corresponding densities
Refractive index b, n20
4 1.540
Vapor pressure log P ¼  (4726.95/T ) þ Temperature,
C Solubility, g/100 g* Relative density d417:5


(solid, 57 – 107 C) 11.3478 kPa
Specific heat cp ¼ 1.084 þ 0.0318 t J/g 0 3.5 1.016
(solid, 200 to 50
C) 10 5.5 1.025
Heat of combustion DH
c (25
C) 245.61 kJ/mol 17.5 8.5 1.038
Standard enthalpy of formation 826.78 kJ/mol 20 9.5
DH
f (25
C) 30 14.5
Standard free energy of formation 697.91 kJ/mol 40 22
DG
f (25
C) 50 32
Heat of solution (in water) 9.58 kJ/mol 60 46
Heat of sublimation 90.58 kJ/mol 80 85
Heat of decomposition 826.78 kJ/mol 90 120
Entropy, S
(25
C) 120.08 J mol1 K1 *
Anhydrous basis.
Vol. 25
and petroleum ether. The ionization constants
show that oxalic acid is a strong acid. The value
of K1 is comparable to that of mineral acids and
the value of K2 corresponds to ionization con-
stants of strong organic acids, for example, ben-
zoic acid.
3. Chemical Properties
In the homologous series of dicarboxylic acids,
oxalic acid, the first member, shows unique
behavior because of the interaction of the neigh-
boring carboxylate groups. This results in an
increase in the value of the dissociation constant
and in the ease of decarboxylation: Upon rapid
heating to 100
C oxalic acid decomposes into
carbon monoxide, carbon dioxide, and water
with formic acid as an isolable intermediate. In
aqueous solution decomposition is induced by
light, and to a much greater extent by g- or X-
rays (to carbon monoxide, carbon dioxide, for-
mic acid, and occasionally hydrogen). This
decomposition is catalyzed by the salts of heavy
metals, for example, by uranyl salts. Oxalic acid
cannot form an intramolecular anhydride. Upon
heating to over 190
C or warming in concen-
trated sulfuric or phosphoric acid, oxalic acid
decomposes to carbon monoxide, carbon diox-
ide, and water: this decomposition is not
exothermic.
Ease of reaction with oxygen is also a typical
characteristic of oxalic acid:
HOOC COOHþ1=2 O2 !2 CO2 þH2 O
This reaction can be exploited in quantitative
analysis (Manganometry, see Chap. 5).
The reducing properties of oxalic acid (which
itself is oxidized to the harmless end products
carbon dioxide and water) form the basis for the
variety of practical applications (see Chap. 6).
Oxalic acid is also oxidized relatively easily to
carbon dioxide by many other oxidizing agents in
addition to air, especially in the presence of the
salts of heavy metals. Oxalic acid is easily ester-
ified, whereby two types, the acidic mono or
neutral diesters can result. These esters are ap-
plied as intermediates in chemical syntheses.
They react relatively easily with water, ammo-
nia, or amines to afford the corresponding acyl
derivatives.
Oxalic Acid 531
Important chemical characteristics are also
demonstrated by the metal salts of oxalic acid.
These exist in two types – the acidic and neutral
salts. The alkali metal and iron ( III) salts are
readily soluble in water. All other salts are spar-
ingly soluble in water. The near complete insol-
ubility of the alkaline-earth salts of oxalic acid,
especially of calcium oxalate, finds some appli-
cations in quantitative analysis. When heated all
these metal salts lose carbon monoxide. Other
salts which are easier decomposable lose carbon
dioxide in addition. The alkali and alkaline-earth
salts form carbonates under these conditions.
Manganese, zinc, and tin salts form oxides; iron,
cadmium, mercury, and copper salts form mix-
tures of oxides and metals. Nickel, cobalt, and
silver salts afford pure metals. Anhydrous fusion
of oxalates with alkali yield carbonates and
hydrogen. For review see [6].
4. Production Processes and Raw
Materials
There are many industrial processes for the pro-
duction of oxalic acid, which have been carried
out by a large number of companies and are in
part still used today. In recent years both the
number of firms producing oxalic acid and the
number of starting materials used for its produc-
tion have been reduced. Generally, only three
classes of compounds are employed as raw ma-
terials for the production of oxalic acid. These
are:
carbohydrates (including ethylene glycol and
molasses)
olefins
carbon monoxide
Nevertheless, three outdated methods, which
have been abandoned in important industrial
nations for economic reasons, are described
briefly [7], because in the third world small firms
might exist that still employ these production
methods:
1. The sodium formate method, which is also
based on carbon monoxide as the raw materi-
al, but involves very cumbersome procedures
of questionable technical safety that are no
532 Oxalic Acid
longer economically feasible (heating to
400
C, elimination of hydrogen, calcium
precipitation, and precipitation with sulfuric
acid). Nevertheless, this process is probably
still being used in China.
2. The alkali fusion of cellulose, which is the
oldest production method [8]. Although cel-
lulose-containing material from every source
can be used in this method, this process has
been discontinued because of the low yields,
large amounts of required alkali and sulfuric
acid, and the large amounts of wastewater.
3. The isolation of oxalic acid as a byproduct of
carbohydrate fermentation, for example, in
the synthesis of citric acid [9]. The process
involves the biotechnical exploitation of the
tricarboxylic acid cycle through enzymatic
cleavage of sugars. The intermediary formed
oxalacetic acid esters and oxalosuccinic acid
(1-oxopropane-1,2,3-tricarboxylic acid) es-
ters are cleaved by hydrolases. Especially
because of the handling of large amounts of
water, this process is no longer economically
feasible.
In all industrial processes, oxalic acid is pro-
duced as the crystalline dihydrate. In the follow-
ing sections four methods are described that are
currently used industrially. Three of them are
based on a nitric acid oxidation and one is a
synthesis using carbon monoxide. A new review
of oxalic acid production from various sources is
given in [10].
4.1. Oxidation of Carbohydrates
This method, the oldest of chemical productions,
was in principal discovered by SCHEELE more
than 200 years ago (1776). He oxidized sugar
with concentrated nitric acid to oxalic acid.
However, it was not until ca. 1940 that this
process gained industrial importance when the
nitrogen oxides produced in the reaction could be
recovered and recycled. In Germany, I.G. Farben
produced 2000 t of oxalic acid per year by this
method until 1944 [11]. This process is employed
in Brazil, China, and in several Eastern European
countries. Raw materials employed in this pro-
cess include sugar, glucose, fructose, corn starch,
wheat starch, reclaimed starch, potato starch,
corncobs, tapioca, and molasses. Choice of start-
Vol. 25
ing material depends on availability and price
and on optimization of the reaction process in-
volved. For example, depending on the starting
materials foam, greases, slime, and varying
yields can be expected and must be dealt with
accordingly [1]. Molasses and other agricultural
waste have gained increasing importance as raw
materials. These materials are not only inexpen-
sive, but must be further processed in any case
due to environmental reasons. Molasses con-
tains, as a production residue of sugar refinement,
many nitrogen-containing compounds, which
are, however, for the most part removed during
the nitric acid oxidation. This explains the diffi-
culties encountered with excessive foam forma-
tion during production that must be overcome. If
starch products are used as raw materials they
must be hydrolyzed to glucose in an extra batch-
wise step prior to the actual oxidation [12], [13].
This is carried out by boiling the starch suspen-
sion in the presence of oxalic acid or sulfuric acid
for about six hours. The oxidation of the resulting
glucose and the following steps are then essen-
tially continuous operations. The oxidation oc-
curs according to the following idealized equa-
tion:
In fact besides NO other nitrogen oxides such
as NO2, N2O, N2O5 are formed.
Allied Chemical Process. The Allied Chemi-
cal process is schematically presented in Figure 1.
The concentration of the glucose solution
obtained by hydrolysis of starch is approximately
50 – 60 wt %. This material, along with the re-
cycled supernatent from the crude centrifugation,
is placed in a reactor with ca. 50 % sulfuric acid,
vanadium pentoxide (0.001 – 0.05 wt %) and
iron (III) sulfate (0.39 – 0.8 wt %), based on the
total mass of the mixture. Nitric acid (65 %) is
then added slowly under vigorous stirring in a
tightly controlled temperature range around
70
C – the temperature range differs according
to the raw material being used. The strongly
exothermic reaction must be well cooled. Air is
simultaneously blown into the reactor to support
the reaction and to remove NO and other nitrogen
oxides of low oxidation number. The nitrogen
oxides expelled are collected in an adsorption
Vol. 25 Oxalic Acid 533

the theoretical yield is obtained. The absent ca.

35 % of the yield mainly results from losses
through CO2 formation. This process is employed
today in Spain, Brazil, The People’s Republic of
China, Taiwan, Korea, and India.

4.2. Oxidation of Ethylene Glycol

The oxidation of ethylene glycol with nitric acid

is a one-step process. A flow chart is shown in
Figure 2. An oxidizing mixture of 30 – 40 %
sulfuric acid and 20 – 25 % nitric acid is used.
The oxidation is carried out in the presence of
vanadium pentoxide and iron (III) salts, at 50 –
70
C and atmospheric pressure. Only CO2 is
formed as a byproduct. This original process has
been improved by the Mitsubishi Gas Company
and in Japan most of the oxalic acid is produced
this way [15]. The improved process operates at
about 10 bar in a pressure reactor, in which ca.

Figure 1. Production of oxalic acid by oxidation of carbo-

hydrates (Allied Chemical process)

system and are recycled after oxidation. Crude

oxalic acid is obtained after cooling and centrifu-
gation of the reaction mixture. The crude acid is
again dissolved in hot water, put through a grease
separator and recrystallized. After a second cen-
trifugation and drying, oxalic acid dihydrate is
obtained with a purity >99 %. Precise control of
the reaction parameters is critical for a good yield
[14]. For good quality raw materials ca. 65 % of Figure 2. Production of oxalic acid from ethylene glycol
534 Oxalic Acid Vol. 25

60 % nitric acid and possibly also sulfuric acid at engineering and construction improvements and
80
C, is pressurized with oxygen at 3 – 10 bar. strict observance of the reaction conditions.
Ethylene glycol is then continually pumped in These refinements increased the yield and solved
and the temperature and pressure are maintained the serious safety problems [17]. Rhône-Poulenc
by addition of oxygen. The exothermic reaction is reputed to be the largest oxalic acid producer in
must be held at a temperature of 50 – 70
C by the world. The two-step process can be repre-
effective cooling. The yield of oxalic acid, based sented by the following equations approximate
on ethylene glycol, is 90 – 94 % of the theoreti- stoichiometry:
cal value. The nitric acid used can be recovered
almost completely. This indicates that the nitro-
gen oxides and nitric acid only act as catalysts
and the actual oxidation has been effected by
oxygen. The idealized overall equation for this
reaction is:

Other suitable starting materials are propylene

glycol, acetaldehyde, or glycolic acid. Vanadium
compounds (0.001 – 0.1 wt %) are recom- Process Description (see Fig. 3). Propene is
mended as promoters. Sodium nitrite, formic introduced into a solution of nitric acid (50 –
acid, or formaldehyde are recommended as in- 75 wt %) in the first reactor at 10 – 40
C, while
itiators [16]. Ube Industries in Japan have further keeping the molar ratio of propene to nitric acid
developed the process so that it operates only at 0.01/1.0 – 0.5/1.0 to produce watersoluble
with nitric acid (no sulfuric acid), however,
pressure is required. In an oxalic acid process
developed in the former Soviet Union a mixture
of nitric and sulfuric acids is used. The reaction is
performed at 1.3 – 4.0 kPa (the pressure is less
than that employed in the Mitsubishi process) to
remove NOx more effectively.
Although the ethylene glycol process clearly
affords the best yields by a wide margin, the corn
starch and molasses oxidations are still more
advantageous from an economic point of view.
Ethylene glycol oxidation is carried out only by
Mitsubishi in Japan.

4.3. Oxidation of Propene

The second most important industrial process for

the production of oxalic acid (after carbohydrate
oxidation) is the reaction of propene with nitric
acid. The worldwide production of oxalic acid by
this method in 1978 was 65 000 t/a. Pure pro-
pene or propene rich fractions from petrochemi-
cal refineries can be used as feedstocks. This
earlier developed reaction was significantly im-
proved by Rhône-Poulenc in France by technical Figure 3. Production of oxalic acid from propene
Vol. 25
intermediates of a-nitratolactic acid and lactic
acid. In the second step the solution of these
partially oxidized products is treated with oxygen
at 45 – 100
C in the presence of a catalyst.
Oxalic acid is formed, crystallized, and filtered.
The overall yield based on propene is claimed to
be ca. 90 % and the conversion of propene is ca.
100 %. The nitrogen oxides are removed from the
second reactor and recovered. The consumption
of nitric acid is 1.2 kg per kg of oxalic acid
dihydrate produced. The process can also be
employed for the production of lactic acid instead
of oxalic acid. An improvement in the yield is
achieved by addition of catalysts (salts or com-
pounds containing Fe, Al, Cr, Sn, Bi, or I). In the
chemical industry chromium (III) nitrate, iron
(III) nitrate or tin (II) chloride are employed in
quantities of 0.4 – 0.5 wt % (based on the metal)
and dissolved in 65 % nitric acid. The scope and
limitations of this process are restricted by safety
problems because the nitrates of a-hydroxycar-
boxylic acids that are formed as intermediates
from a-olefins and NO2 are unstable and lead to
uncontrollable decomposition and violent explo-
sions [18]. As a result many technical difficulties
need to be overcome to carry out these processes.
Today this process is only operated by Rhône-
Poulenc. Analogous to propene, ethylene can
also be oxidized to oxalic acid.
4.4. Production from Carbon
Monoxide [19], [20]
The newest process for the industrial production
of oxalic acid was developed by Ube Industries.
Their synthesis is performed in two steps. In the
first step CO and a lower alcohol are reacted
under pressure and in the presence of a catalyst to
form the corresponding diester of oxalic acid.
This diester is hydrolyzed in the second step to
oxalic acid and the original alcohol which is then
recycled. Palladium on charcoal and alkyl nitrites
are employed as catalysts and the reaction is
carried out at 10 – 11 MPa. n-Butanol is the
preferred alcohol and is simultaneously used as
the solvent. This process has the advantage of
inexpensive starting materials, however, it is
disadvantageous with regard to the much higher
capital investment (high pressure) and utility
costs.
Oxalic Acid 535
New perspectives and developments are given
in [21]. The use of palladium catalysts is dis-
cussed in [22].
The catalytic action of the alkyl nitrite on the
first reaction is believed to be the following:
2 RONOþ2 CO!ðCOORÞ2 þ2 NO ð3Þ
2 NOþ1=2 O2 þ2 ROH!RONOþH2 O ð4Þ
Butyl nitrite and methyl nitrite are the pre-
ferred alkyl nitrites for industrial purposes. The
first plant using butyl nitrite in the production of
oxalic acid was constructed in 1978 (6000 t/a
oxalic acid). The advantages of using butyl nitrite
are as follows:
1. It functions not only as reaction component
but also as a dehydrating agent. Butyl nitrite
has a higher boiling point than water and butyl
nitrite and water form an azeotropic mixture
with a lower boiling point than butyl nitrite.
Thus, the water formed can be removed as an
azeotropic mixture and most of the butyl
nitrite remains in the system. Butyl nitrite is
recovered from the azeotropic mixture and
reused.
2. Butyl nitrite is finally hydrolyzed to butanol
which can easily be separated from oxalic acid
solution by phase separation.
A flow chart of the process using butyl nitrite
is given in Figure 4. A circulation liquid contain-
ing butyl nitrite, butanol, and the palladium
catalyst and a circulation gas containing carbon
monoxide and oxygen are pressurized and fed to
a reaction tower. Here dibutyl oxalate is formed
and butyl nitrite is consumed (Eq. 3). Butyl
nitrite is regenerated simultaneously (Eq. 4).
Both reactions are exothermic. The selectivity
for dibutyl oxalate increases with increasing
reaction pressure and decreasing reaction tem-
perature; however, the velocity of the reaction
increases with increasing temperature. Thus, the
536 Oxalic Acid
Figure 4. Production of oxalic acid from carbon monoxide
an butanol using butyl nitrite as catalyst
reaction is conducted industrially at 10 –
11 MPa and 90 – 100
C.
Gas circulation is carried out in order to hold
the oxygen concentration below the explosion
limit during the reaction and to improve the
carbon monoxide utilization and gas–liquid con-
tact rate.
The solution released from the tower is flashed
to evaporate the carbon dioxide gas formed as a
byproduct. The reaction water is removed by
azeotropic distillation with butyl nitrite and most
of the solution is recycled to the reaction tower.
Part of the solution is further processed: it is first
Vol. 25
filtered to separate the catalysts; then butyl
nitrite, and butanol are removed to yield pure
dibutyl oxalate. The palladium catalyst, butyl
nitrite, and butanol are recovered and returned
to the circulation liquid, which is also supplied
with make-up butanol and nitric acid. The circu-
lation liquid is then pressurized and fed back to
the reaction tower.
The refined dibutyl oxalate is mixed with the
mother liquor from the oxalic acid crystallization
and hydrolyzed at about 80
C into oxalic acid
and butanol. The oxalic acid solution and butanol
are separated by phase separation. Then oxalic
acid dihydrate is crystallized from the oxalic acid
solution, and butanol is recycled to the process
after refining. A gas-phase process using methyl
nitrite has been established [21], [22]. This pro-
cess employs a lower reaction pressure (390 kPa)
and is more economic than the liquid-phase
method because of the following reasons:
1. The consumption of electric power is greatly
reduced owing to the low pressure operation
(about 60 % saving).
2. Dimethyl oxalate formation and methyl ni-
trite regeneration reaction are separated;
hence, side-reactions are decreased and the
yield of dimethyl oxalate is increased (98 %).
3. Inexpensive methanol is used instead of
butanol.
4.5. Production of Anhydrous Oxalic
Acid
In all processes oxalic acid is obtained as the
dihydrate. Anhydrous oxalic acid can be ob-
tained by heating oxalic acid dihydrate to ca.
3
C below its melting point or by azeotropic
distillation with benzene or toluene. The demand
for anhydrous oxalic acid is, however, very low.
5. Chemical Analysis
Qualitative Analysis. Upon heating oxalic
acid with diphenylamine a blue color results, the
so-called ‘‘aniline blue’’. Analysis limit: 5 mg
[23].
Quantitative Analysis. In addition to sim-
ple acid–base titration, which of course can only
Vol. 25
be conducted in the absence of other acids, four
important analytical methods exist.
Manganometry. As the reaction of oxalic
acid and KMnO4 is quantitative, oxalic acid can
be easily titrated with a standard solution of
KMnO4.
5 ðCOOHÞ2 þ2 KMnO4 þ3 H2 SO4 !
K2 SO4 þ2 MnSO4 þ10 CO2 þ8 H2 O
This method can only be used in the absence
of other reducing agents.
Gravimetry. Because of the insolubility of
calcium oxalate in water (100 g of water at 18
C
dissolves only 0.0006 g of calcium oxalate),
oxalic acid can be very easily and quantitatively
precipitated out of aqueous solutions, e.g., with
calcium chloride. The oxalic acid content of the
precipitate is determined either gravimetrically
(after ashing as CaO) or manganometrically.
Determination by HPLC. In this determina-
tion the oxalic acid must be esterified, separated
by HPLC and analyzed by gas chromatography
subsequently [24].
Enzymatic Determination. This method is
usually used for analysis of oxalic acid in bio-
logical material, such as in fruit or vegetables and
in body fluids. Either oxalate oxidase [25], [26],
oxalate decarboxylase, or formate dehydroge-
nase are employed [27].
6. Uses
Apart from the application of oxalic acid as a
synthetic intermediate, the properties of oxalic
acid or its salts have generally been exploited as
reducing agents (in which case the harmless final
products of carbon dioxide and water are formed),
as precipitants for calcium ions, or as complexing
agents for the salts of heavy metals. The principal
applications worldwide can be divided into the
following groups in percentages of total use:
Metal treatment ca.
Textile treatment ca.
Bleaching agents ca.
Chemical uses ca.
Oxalic Acid 537
6.1. Metal Treatment
Sodium, potassium, or ammonium oxalates form
soluble double salts with heavy metals, especial-
ly iron. Iron (III) oxalate is the only readily
soluble heavy metal salt. Oxalic acid salts are
therefore used (1) for rust removal, e.g., from
cooling systems (automobile radiators), boilers,
or from steel plates before phosphating, (2) for
removal of iron veins in marble, (3) as a constit-
uent of metal cleaners with rust protection, espe-
cially for use on copper, silver, or aluminum, (4)
in anodizing of aluminum, for the formation of
very hard, abrasion and corrosion protective
coatings, where through the use of additives
different surface colors can be imparted to alu-
minum [28], [29]. Oxalic acid is also used for the
cleaning of materials for electronic devices, and
as coatings for protection of stainless steel, nickel
alloys, chromium, alloy steels, and titanium [30],
[31].
6.2. Textile Treatment
Oxalic acid is used as mordant for the printing
and dyeing of wool and cotton. It serves as a
stripping agent for wool colors for special pat-
tern affects, as auxiliary in indigo caustic dis-
charge printing, and is used in vat dyeing as a
reducing agent for potassium dichromate. In
laundries oxalic acid is used for the removal of
rust stains and the neutralization of alkalinity. It
also has an antibacterial effect [32]. Oxalic acid
can be employed as a catalyst for cross linking of
textile finishing agents in the permanent press-
ing of cellulose fabrics and for flameproofing
[33].
6.3. Bleaching Agents
Oxalic acid is used in the tanning and bleach-
ing of leather, and in bleaching of cork, wood
(especially veneered wood), straw, cane, feath-
ers as well as natural and synthetic waxes. The
28 % majority of oxalic acid is used for the bleach-
25 % ing of pulpwood. In leather processing oxalic
20 %
27 %
acid is used in whitening instead of sodium
dithionite.
538 Oxalic Acid
6.4. Chemical Uses
Preparation of Esters and Salts. Because
of the two carboxyl groups oxalic acid forms acid
esters and salts as well as normal esters and salts.
Reagent in Chemical Synthesis. Since oxa-
lic acid is a strong dehydrating agent it can be
used in condensation reactions, in the esterifica-
tion of secondary alcohols to esters, or in cycli-
zation reactions [34].
Concentration of Rare Earth Elements.
Oxalic acid is used for the concentration and
isolation of rare earth elements from aqueous
solutions that are formed during the digestion of
lanthanide ores (for example, monazite) with
sulfuric, hydrochloric, or phosphoric acids. The
precipitation of oxalates is almost quantitative
even from strongly acidic solutions. After pre-
cipitation the oxalates are converted to their
oxides by heating and processes further in this
form [35], [36].
Other Uses. Small particles or powders,
which are prepared from oxalates, are used for
magnetic recording tapes. Oxalic acid is used for
the preparation of polyester oxalates and copo-
lyoxamides [37], [38]; for the production of inks,
pigments, and paints [39]; and for the preparation
of catalysts especially those which contain pre-
cious metals and as redox initiators.
7. Economic Aspects
China is by far the largest producer, consumer,
and exporter of oxalic acid worldwide, because
of a large rare earth oxides market. World capac-
ity for oxalic acid increased by ca. 190  103 t
during 2007–2009, all growth occurring in China
[40].
8. Storage, Handling,
Transportation, Waste Disposal
Dry oxalic acid is packed and sold in polyethyl-
ene lined multilayered bags or in polyethylene or
poly(vinyl chloride) vessels or drums. Rein-
forced fiberglass plastics are also used commonly
and are recommended for storage.
Vol. 25
Oxalic acid is not flammable and also not self
inflammatory up to 400
C. It is not shock
sensitive and does not cause dust explosions.
Oxalic acid is a weakly dangerous substance for
water (hazard class 1) and exhibits low toxicity
for fish and bacteria. Labelling according to
Gef Stoff V: Xn (less poisonous). R-phrase:
21/22 (dangerous to health through contact with
the skin and through ingestion); S-phrase: 2, 24/
25. For inhalation protection masks with fine
particle filters (filter class P 2) and protective
gloves made from PVC or rubber are recom-
mended [41].
Neither oxalic acid nor its solutions should be
discarded in the environment before proper treat-
ment. Common treatments include incineration
or heating with sulfuric acid to convert it to
carbon monoxide, carbon dioxide, and water.
Small amounts of oxalic acid can be treated with
potassium permanganate to give carbon dioxide.
Neutralization with lime results in precipitation
of insoluble calcium oxalate. The latter can be
safely deposited.
9. Derivatives
9.1. Salts
In addition to neutral and acid salts, oxalic acid
also forms many complex compounds that easily
crystallize. Simple oxalates of nearly all organic
and inorganic bases are known. The three most
important salts of oxalic acid are potassium
hydrogen oxalate (salt of sorrel), ammonium
oxalate, and ammonium iron (III) oxalate. All
other salts of oxalic acid are less important
industrially.
Potassium Oxalate [583-52-8], K2C2O4 
H2O, Mr 184.24, has the highest water solubility
of any neutral oxalate (at 20
C, 25 wt %). It was
formerly used for the preparation of photograph-
ic developers and is employed today in the
production of uranium in the extraction of the
so-called yellow cake and in metal and textile
treatment.
Potassium Hydrogen Oxalate [127-95-7],
KHC2O4  H2O, Mr 146.15, is found in many
plants and was the first oxalate discovered in
nature. LDLo, oral, human: 660 mg/kg.
Vol. 25
Ammonium Oxalate [1113-38-8],
(NH4)2C2O4  H2O, Mr 142.08. The anhydrous
salt dissolves in water at 0
C up to 2.27 wt % and
at 100
C up to 25.8 wt %. Ammonium oxalate is
used in textile and leather processing as a replace-
ment for oxalic acid, for the precipitation of rare
earth elements, and in ore beneficiation (precipi-
tation of heavy metals from acidic extracts).
Ammonium Iron (III) Oxalate [13268-42-
3], (NH4)3[Fe(C2O4)3]  3H2O, Mr 428.08,
forms emerald green crystals and is readily solu-
ble in water and sensitive to light. It is used in the
anodizing of aluminum and imparts, dependant
on concentration, either yellow, gold, or brown
colorations to aluminum. It is also employed in
the treatment of other metals.
Sodium Oxalate [62-76-0], Na2C2O4, Mr
134.01, is easily prepared in high purity from
oxalic acid and sodium hydroxide. Therefore, it
is used as a titrimetric standard substance. The
solubility in water at 0
C is 2.6 wt % and at
100
C is 6.3 wt %. Sodium oxalate is used for
the production of super white pulp.
9.2. Organic Derivatives
(Cyanogen ! Cyano Compounds,
Inorganic)
Esters. Oxalic acid can be easily esterified
by the usual methods. It forms both neutral
(ROOCCOOR) and acidic esters (ROOC
COOH). The inherent acidity of oxalic acid is
sufficient to catalyze the esterification in most
instances. In some cases the esterification stops at
the monoester stage. In this case anhydrous
oxalic acid is used in preparation of the diester.
Newer methods include the preparation from
carbon monoxide and alcohols according to the
Ube process (see Section 4.4) and the reaction of
the easily accessible oxamide (see below) with
Table 2. Physical properties of selected oxalates
Ester Mr mp,
C
Dimethyl 118.09 54
Diethyl 146.15 40.6
Di-n-butyl 202.15 29.6
Oxalic Acid 539
alcohols in the presence of concentrated sulfuric
acid [42].
Of industrial interest are the neutral esters,
especially dimethyl, diethyl, and di-n-butyl ox-
alates. Except for the dimethyl ester which is a
solid at room temperature they are all oily liquids
with a faint odor, and thermally stable. Some
esters can be distilled at atmospheric pressure
without decomposition. The esters are readily
soluble in alcohols, benzene, diethyl ether, ace-
tone, and dioxane. Selected physical properties
are presented in Table 2. The neutral esters are
good solvents for ethers and esters of cellulose
(e.g., nitrocellulose) and for resins. They are
therefore used for the production of special lac-
quers. Of greatest significance is the diethyl ester.
The di-n-butyl ester is also used as a plasticizer.
A further application results from the ability of
oxalic acid esters to easily undergo condensation
reactions. Especially diethyl oxalate plays an
important role in organic synthesis.
Oxamide [471-46-5], H2N-OC-CO-NH2,
Mr 88.07, mp ca. 350
C (decomp.), is sparingly
soluble is water (0.3 g/L at 20
C; 6 g/L at
100
C).
The most economic method for the production
of oxamide is a one-step process by Hoechst that
is based on a catalytic oxidation of hydrogen
cyanide [43]:
The flow .chart is shown in Figure 5. A solu-
tion of copper nitrate in aqueous acetic acid is
employed as the catalyst. The reaction is run at
65
C and the yield is nearly quantitative. The
oxamide that is insoluble in the catalytic solution
precipitates at the bottom of the reactor and is
pumped from there to a centrifuge, washed,
bp,
C d420 CAS registry no.


163.5 1.148 (54 C) [553-90-2]
184.4 1.0785 [95-92-1]
245.5 0.9873 [2050-60-4]
540 Oxalic Acid
Figure 5. Continuous production of oxamide a) Reactor;
b) Cooler; c) Sludge pump; d) Centrifuge; e) Dryer;
f) Granulator
dryed and, if desired, granulated. Without further
treatment it has a purity of >99 % [44]. Using this
method Enimont in Gela/Sicily, began a produc-
tion plant in 1990 with a capacity of 10 000 t/a
[45].
Oxamide can be converted to ammonium
oxalate and oxalic acid by heating it for long
periods with water; best results are obtained by
the application of pressure. Oxamide has proved
to be of great interest as a long-term fertilizer
(! Fertilizers, 1. General). A single application
is sufficient because the nitrogen is released
gradually throughout the vegetation period in a
form that the plant can easily use. A granular
application form of oxamide is required. The
poor aqueous solubility of oxamide guarantees
that the fertilizer will not be washed away by
Vol. 25
rainfall and that it can be used in rice plantations.
Oxamide can also be used as a starting material
for chemical syntheses.
10. Toxicology [46], [47]
Like other strong acids, oxalic acid has a local
caustic effect. The compound is absorbed rela-
tively well through the skin and very well
through mucous membranes, so that contact with
larger amounts can quickly lead to absorptive
poisoning. Oral ingestion causes acute irritation
and pain in the mouth, esophagus, and stomach.
Nausea, vomiting of blood, collapse, convul-
sions, irritability, and cramps (calcium precipi-
tation) are known to occur. Premature coronary
and/or circulatory arrest, and/or a kidney mal-
function which results in anuria and uremia are
possible. Eventual transition to polyuremia can
occur. Death occurs in the coma or through
kidney failure. Workers who had contact with
a 5 % solution of oxalic acid without wearing
protective gloves, complained of pains in their
hands within a few days. Blood clots and dam-
aged blood vessels and finally a very painful
gangrene made amputation of the fingers neces-
sary. With solutions of higher concentrations the
superficial caustic effects become increasingly
significant. Inhaling the vapors and/or dust
evokes responses that range from irritation of
the mucous membranes to rashes, headaches,
overexcitability, and albuminuria. Persistent
coughing, vomiting, and general weakness are
signs of chronic effects. Skin rashes and brittle
yellow fingernails are also known.
Intake of food containing higher quantities of
oxalic acid should be avoided because of an
impaired calcium absorption through the forma-
tion of insoluble calcium oxalate: 4 – 5 g oxalic
acid can be deadly for humans because the
precipitated calcium oxalate plugs the kidney
channels. The normal excretion of oxalic acid
from humans is 20 mg per day. Two-thirds of all
kidney stones are composed of calcium oxalate.
The toxicological levels are [48]:
LD50, oral, rat 375 mg/kg
LDLo, oral, human 71 mg/kg
RTECS-no. Ro 245000
EC-no. 607–006–00–8
Vol. 25
References
1 Kirk-Othmer, 3rd ed., 16, 618 – 636.
2 R. Schr€ oder, DMW Dtsch. Med. Wochenschr. 105 (1980)
997.
3 R. C. West (ed.): CRC Handbook of Chemistry and
Physics, 61st ed., CRC Press, Boca Raton, FL, 1980.
4 H. T. Clarke, A. W. Davis: Organic Syntheses, 2nd ed.,
coll. vol. I, J. Wiley and Sons, New York 1946, pp. 421 –
425.
5 W. Riemenschneider: unpublished results.
6 D. Dollimore, Thermochim. Acta 117 (1987) 331 – 363.
7 Ullmann, 4th ed., 17, 476, 477.
8 Ullmann, 4th ed., 17, 478, 479.
9 Ullmann, 4th ed., 17, 479.
10 S. K. Dube et al., J. Chem. Technol. Biotechnol. 32 (1982)
no. 10, 909 – 919.
11 BIOS final report no. 663, 1946.
12 Allied Chem., US 2 057 119, 1936 (G. S. Simpson).
13 Allied Chem., US 2 322 915, 1943 (M. J. Brooks).
14 Allied Chem., US 3 536 754, 1970.
15 Mitsubishi Gas, US 3 691 232, 1972 (E. Yonemitsu
et al.).
16 Mitsubishi Gas, DE 2 011 998, 1969.
17 Allied Chem., US 3 081 345, 1963 (E. J. Carlson, E. E.
Gilbert).
18 H. Saito, Shokubai 23 (1981) no. 2, 139 – 142; Chem.
Abstr. 95 (1981):79382u.
19 S. Uchiumi, Y. Masayosi, J. Japan Petrol. Inst. 25 (1982)
no. 4, 197 – 204.
20 D. M. Fenton, P. J. Steinwand, J. Org. Chem. 39 (1974)
701.
21 Rhône-Poulenc, DE 1 618 824, 1967.
22 A. M. Gaffney et al., Chem. Ind. (Dekker) 33 (1988) 87 –
100.
23 F. Feigl et al., Mikrochemie 18 (1935) 272.
24 S. M. Steinberg et al., Int. J. Environ. Anal. Chem. 19
(1985) 251 – 260.
25 U. Rehmert et al., Lab. Med. 7 (1983) 29 – 32.
26 J. E. Buttery et al., Clin. Chem. (Winston-Salem N.C.) 29
(1983) 700 – 702.
27 H.-O. Beutler et al., Z. Anal. Chem. 301 (1980) 186.
28 S. Werneck, R. Pinner: The Surface Treatment and Fin-
ishing of Aluminum and its Alloys, R. Draper Ltd.,
Teddington 1972.
29 S. John, B. A. Shenoi, Met. Finish 74 (1976) no. 9, 48, 57.
30 P. E. Morris, Corrosion (Houston) 33 (1977) 17.
Oxalic Acid 541
31 W. Widerholt: The Chemical Surface Treatment of Me-
tals, R. Draper Ltd., Teddington 1965.
32 H. Cohen, G. E. Linton: Chemistry and Textiles for the
Laundry Industry, Textile Book Publishers Inc., New
York 1961.
33 N. A. Cashen et al., US 3 811 210, 1974.
34 L. Re, B. Maurer, T. Ohloff, Helv. Chim. Acta 56 (1973)
1882.
35 L. A. Sarrer et al., J. Am. Chem. Soc. 49 (1972) 943.
36 G. M. Varshal, Metody Khim. Anal. Khim. Sostav Miner.,
1971, 18 – 33; Chem. Abstr. 75 (1971) : 133488k.
37 A. Alsnis et al., Latv. PSR Zinat. Akad. Vestis 5 (1976)
81 – 90; Chem. Abstr. 85 (1976) : 78382a.
38 O. Vogl et al., Polym. Prepr. (Am. Chem. Soc. Div. Polym.
Chem.) 19 (1978) no. 2, 75 – 80.
39 N. H. Andersen et al., Synth. Commun. 3 (1973) 125.
40 http://www.sriconsulting.com/CEH (accessed 28 June
2010) .
41 GefStoffV of Aug. 28th, 1986.
42 R€ohm GmbH, DE 1 668 639, 1967 (W. Gruber, J.
Dehler).
43 Hoechst AG, DE 2 308 941, 1973 (W.
Riemenschneider).
44 W. Riemenschneider, Chem. Ing. Tech. 50 (1978) 55.
45 Chem. Ind. 7 (1989) 18.
46 N. I. Sax: Dangerous Properties of Industrial Material,
6th ed., Van Nostrand Reinhold, New York 1984, p. 2098.
47 K€uhn-Berett: Merkbl€ atter Gef€
ahrliche Arbeitsstoffe 12/
1982, Verlag Moderne Industrie, M€unchen 0–03–1/2.
48 Registry of Toxic Effects of Chemical Substances, US
Department of Health and Human Services, Cincinnati,
Ohio 1983/1984.
Further Reading
A. D. Covington: Tanning Chemistry, Royal Society of
Chemistry, Cambridge, UK 2009.
P. J. O’Brien, W. R. Bruce (eds.): Endogenous Toxins, Wiley-
VCH, Weinheim 2010.
H. Sawada, T. Murakami: Oxalic Acid, ‘‘Kirk Othmer
Encyclopedia of Chemical Technology’’, John Wiley &
Sons, Hoboken, NJ, online DOI: 10.1002/
0471238961.1524011219012301.a01.
A. S. Tracey, G. R. Willsky, E. Takeuchi: Vanadium, CRC
Press, Boca Raton, FL 2007.