CARBON

4 8 ( 2 0 1 0 ) 1 0 3 2 1 0 3 7

available at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/carbon

Evidence for the presence of cyanide during carbon

activation by KOH
E. Fuente a, R.R. Gil a, R.P. Giron a, M.A. Lillo-Rodenas b, M.A. Montes-Moran
M.J. Martin c, A. Linares-Solano b

a,*
,

Instituto Nacional del Carbon, CSIC, Apartado 73, E-33080 Oviedo, Spain
Grupo de Materiales Carbonosos y Medioambiente (MCMA), Departamento de Qumica Inorganica, Universidad de Alicante,
Apartado 99, E-03080 Alicante, Spain
c
Labotarori dEnginyeria Qumica i Ambiental (LEQUIA), Institut de Medi Ambient, Facultat de Cie`ncies, Universitat de Girona,
17071 Girona, Spain
b

A R T I C L E I N F O

A B S T R A C T

Article history:

The observation that carbon activation by KOH gives rise to a significant formation of cya-

Received 27 July 2009

nide moieties is confirmed. However, contrary to what has been reported, our results show

Accepted 9 November 2009

that the N2 used as an atmosphere during the activation process has little to do with the

Available online 12 November 2009

formation of such cyanide moieties. The main source of cyanides is ascribed to structural
nitrogen already present in the precursors. Reducing species (H2 and metallic K) formed
during the KOH carbon activation process might promote the transformation of that structural nitrogen to cyanides. In order to minimise cyanide formation (and related environmental concerns), materials with low nitrogen content should be selected as precursors
for the preparation of KOH-activated carbons.
 2009 Elsevier Ltd. All rights reserved.

1.

Introduction

Research carried out using alkaline hydroxides as activating

agents for different carbon precursors has been profusely reported. NaOH and KOH activation makes possible activated
carbons with rather unique textural properties, i.e., extremely
high apparent specific surface areas (SBET values as high as
4000 m2 g1 being eventually claimed) and pore volumes.
Thus, chemical activation with hydroxides has become a
recognised method to obtain the sometimes referred to as
super activated carbons [18].
The growing interest on alkaline activation has also
prompted several studies to better understand the mechanism involved. It is now well-established that different chemical pathways occur depending on the nature of the precursor,
raw materials (i.e., lignocellulosic materials) on one side [9],
and carbonaceous precursors (chars, coals, etc.) on the other

[1,1012]. For this latter type of carbon precursors, the following redox mechanism has been proposed from the reaction
products observed during activation performed at temperatures around 750 C [1,1012]:
6MOH 2C ! 2M2 CO3 2M 3H2

M being K or Na. This chemical reaction accounts for the C

oxidation that should develop the porous network in the
remaining carbon material.
In principle, chemical reactions involving other elements
than C (heteroatoms) should be also prone to occur during
the activation, as far as they are present in the precursor. Research contributions on the possible evolution of those other
elements during alkaline activation are scarce, apart from the
interesting recent work of Robau-Sanchez et al. [13,14] where
evidence of cyanide formation during the KOH activation of a
Quercus agrifolia char has been reported. These authors found

* Corresponding author: Fax: +34 985 297662.

E-mail address: miguel@incar.csic.es (M.A. Montes-Moran).
0008-6223/$ - see front matter  2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2009.11.022

CARBON

4 8 ( 20 1 0 ) 1 0 3 210 3 7

that considerably more cyanide was formed under nitrogen

than under argon, leading to the conclusion that cyanide
was produced mainly from N2. These unexpected results are
very surprising in view of the kinetic stability of dinitrogen.
Additionally, they are not in agreement with what was reported in Refs. [1,15], where the effect of the type of gas used
during alkaline activations on the textural properties of the
activated materials was analysed. It was concluded that,
independently of the nature of the gas used (He, Ar or N2),
they only work as purging gases, displacing the global chemical activation reaction towards the products.
In a series of recent contributions, using alkaline hydroxide activation of sludge-based precursors [1619], cyanide
moieties were detected in the activated materials [17,19],
which confirms the results of Robau-Sanchez et al. [13,14].
Such confirmed cyanide formation requires further studies
because of its importance for environmental protection.
Thus, the aim of the present paper is to delve into the causes
of the cyanide formation. For that purpose, precursors with
different nitrogen contents have been selected to address
the contribution of the two possible N sources to cyanide formation: structural nitrogen, or nitrogen coming from the
flowing gas as suggested by Robau-Sanchez et al. [13,14].

1033

The oxygen content determination corresponds to the total

content, i.e., including the metal oxides (ash).

2.2.

Cyanide analysis

2.

Experimental

Six grams of the activated mixtures were split in two parts,

for duplicate analysis. Each part weighing 3 g was washed
with 80 ml of deionised water (MilliQ) in four (20 ml) successive stages, at room temperature. The supernatant liquid was
collected by centrifugation of the solid suspensions. The four
aqueous solutions obtained in every washing plus centrifugation step were finally mixed. pH of the aqueous solutions
were measured using a TIM870 titration system from
Radiometer.
Total cyanide contents of the two duplicate solutions per
sample (80 ml each) were quantified combining the US EPA
9014 [20] and 9010C methods [21]. Basically, cyanides are released from the aqueous solutions as hydrocyanic acid
(HCN), by means of a reflux-distillation operation under acidic
conditions, and absorbed in a scrubber containing sodium
hydroxide solution. Interferences are mostly eliminated
by using this distillation procedure [21]. The cyanide concentration in the absorbing solution was then determined [20]
using a UV 2401PC UVvis recording spectrophotometer
(Shimadzu).

2.1.

KOH activation

3.

Chars were prepared from selected residues attending to

their nitrogen content: a lignocellulosic (Quercus Robur) saw
dust (QUE), two chromium-free solid wastes from the leather
industry (CUA and CUB) and two sewage sludges (SB and
BIOS) collected at two different Spanish wastewater treatment plants (WWTP). SB sludge has been used in previous
works ([1619]). The BIOS sludge was collected directly from
the aeration tank of the activated sludge unit (Girona
WWTP).
Char precursors were obtained from the pyrolysis of the
abovementioned residues for their subsequent activation process study. Approx. 20 g of dried residue were put into an alumina crucible and placed in a ceramic tubular furnace (55 mm
i.d.). The residue was heated up to 750 C in 150 ml min1 of
flowing nitrogen, using a heating rate of 5 C min1. The maximum temperature was held for 60 min. Then, the samples
were allowed to cool down to room temperature in the same
atmosphere (N2). Precursors (chars) were finally ground and
sieved to obtain a particle size smaller than 212 lm, before
proceeding to their chemical activation. Nomenclature used
for the chars is the same as that used for their precursors
adding, at the end, -P.
Powdered KOH (Aldrich) was selected as activating agent.
Approx. 15 g of KOH/precursor mixtures prepared using various weight ratios were placed into an alumina crucible and
heated up to 750 C, using 5 C min1 heating rate and 1 h of
dwelling in the same horizontal furnace used for pyrolysis.
The activation process was carried out in N2 or Ar at different
flow rates.
The analysis of major elements (C, H, N, S and O) of
solid samples was performed as described elsewhere [16].

Results and discussion

The elemental compositions of the five selected residues and

their corresponding chars are collected in Table 1. As mentioned in the experimental section, the N content of the different residues spans a relatively wide range of values, from
less than 1% for the lignocellulosic residue QUE to more than
10% for the CUA sample. In terms of their inorganic (ash) content, the residues could be grouped in two sets, with the QUE
and CU* samples (especially CUA) having very low ash contents and the sludges having relatively high contents (around
30%). After pyrolysis, the initial range of N contents shortens,
especially if daf values are considered. The nitrogen content
in the pyrolysed samples (precursors) is assumed to be linked
to the carbon-rich (char) fraction of the materials, since any
inorganic nitrogen species in the original residues should
not withstand the thermal treatment.
It is confirmed, in agreement with Refs. [13,14,17,19] that
cyanide species were produced in all activation experiments,
regardless of the precursor and conditions employed. They
were analysed indirectly by washing the activated mixtures
using water at room temperature. Preliminary tests (results
not shown) allowed us to conclude that four washing steps
(as described in Section 2) were enough to virtually attain
the complete transfer of the different cyanide moieties,
mainly KCN, to the aqueous solutions. Table 2 shows the cyanide concentration of the solutions obtained when washing
activated mixtures prepared using 1/1 KOH/precursor weight
ratios, under nitrogen. The repeatability of the washing procedure within a given sample was excellent in all cases.
Henceforth, for each activation experiment, only average concentration values obtained from the two measurements will
be reported. For two of the samples, namely CUA-P and

1034

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4 8 ( 2 0 1 0 ) 1 0 3 2 1 0 3 7

Table 1 Elemental analysis (dry basis) of the residues and corresponding chars.
Sample

QUE
CUA
CUB
SB
BIOS
QUE-P
CUA-P
CUB-P
SB-P
BIOS-P
a

Ash content

Elemental analysis (wt.%)

(wt.%)

<0.5
1
2.6
35.9
29.7
2.3
2.9
12.8
72.9
64.5

48.7
51.8
48.2
30.7
39.5
93.0
86.1
80.2
19.2
33.7

6.1
5.6
5.8
4.8
5.6
1.4
1.0
1.0
0.5
0.6

O
a

0.2
10.2
7.5
5.8
6.4
0.8
8.9
6.0
2.6
3.1

42.8
35.3
33.2
24.2
29.7
2.8
4.3
3.5
17.4
20.6

nd
0.3
1.9
1.1
0.9
nda
0.1
1.0
0.5
0.9

Not detected.

Table 2 Cyanide contents of the two washing solutions tested.

Precursor

QUE-P
CUA-P
CUB-P
SB-P
BIOS-P
a
b

[CN] (mg l1)a

[CN-] (mg g1)b

#1

#2

#1

#2

134.8
1842.4
1571.1
308.1
395.2

139.1
1815.2
1558.4
304.9
381.4

3.3
128.5
73.1
28.4
18.2

3.4
128.2
72.3
28.1
17.6

Per litre of aqueous solution.

Per gram of precursor.

CUB-P, cyanide concentrations as high as almost 2 g per litre

of the aqueous solution were obtained. This fact should be taken into account when assessing risks for KOH activation of
precursors having high N contents.
It must be noticed that textural characterisation of the precursors or the activated materials is not included here, since
is out of the scope of the present study. The experimental procedure that has been carried out to quantify the amount of
cyanides formed is different from other, more effective, washing methodologies that are normally required to fully develop
the porosity of the activated samples (e.g., use of HCl to remove the excess of K2CO3). Nevertheless, the activation process takes place as expected (see, for example, the
activation results of SB sludge in [1619]).
It seems clear, from the data of Tables 1 and 2, that the
amount of cyanide detected in the aqueous solutions is higher for the char precursors having higher nitrogen contents
(which in fact also corresponds to the pristine precursors having higher N contents). This seems to indicate that the N2 gas
used as activation atmosphere should have little effect on the
cyanide formation. To confirm and strength this idea, it was
then decided to perform similar experiments under Ar. Identical batches of precursors were employed for both Ar and N2
activation. Results obtained are shown in Fig. 1.
Changing the activation atmosphere has no significant effect on the amount of cyanides detected, which underlines
that the nature of the flowing gas is not responsible for the
formed cyanide. Differences between concentration results
obtained under the two gases (N2 and Ar) are less than 10%

BIOS-P

Ar
N2

SB-P

CUB-P

CUA-P

QUE-P
0

20

40

60
-

80

100

120

-1

[CN ] (mg g )

Fig. 1 Comparison between the amount of cyanides

obtained during the activation of the different precursors
under N2 and Ar.

of their average value. Since reproducibility between two activation experiments is somehow hampered by the hydration/
carbonation of KOH, those differences must be considered
within experimental error. The fact that more cyanides were
detected for two of the precursors (BIOS-P and CUB-P) when
the activation was carried out under Ar further corroborates
this. These results highlight that, considering environmental
concerns, materials with low nitrogen content should be chosen as precursors for KOH activation.

CARBON

Other important issue that should be addressed when

dealing with alkaline hydroxide activation of carbons is the
effect of both nitrogen flow rate and the KOH/precursor ratio.
Two of the precursors under study, namely SB-P and CUB-P,
were selected to carry out additional experiments using different activation conditions. Labelling of the new samples
obeys the following rationale: A/B, A being the flow rate (in
ml min1) and B being the KOH/precursor weight ratio. Results are shown in Figs. 2 and 3.
Figs. 2 and 3 confirm that the precursor with higher nitrogen content leads to higher cyanide amounts and that both
char precursors behave similarly. Although differences are
not very pronounced, it seems that an increase in the carrier
gas flow rate or in the relative proportion of the activating
agent produces, interestingly, solutions with a higher concentration of cyanides. This observation has not been reported
before, as far as Robau-Sanchez et al. failed to find any relationship between the activation conditions and the amount
of cyanides detected [13].
A nitrogen mass balance study was carried out to better
understand the effect of the activating conditions on the formation of cyanides. Elemental analyses of the water-washed
samples were carried out to determine the nitrogen remaining in the activated solids after cyanide removal. Results are
shown in Table 3, keeping a constant basis for the calculations (100 g of precursor). The increase of the CN concentration in the aqueous solutions obtained when activation is
carried out at higher flow rates or KOH/precursor ratios (Figs.
2 and 3, and NL values in Table 3) are attained at the expense
of the nitrogen remaining in the washed solids, so to keep the
amount (Ns,f + NL) relatively constant for a given precursor,
regardless of the activation conditions.
Having more CN transferred from the activated solids to
the aqueous solution when the activation is carried out under
higher flow rates or activating agent/precursor ratios could be
due not only to the formation of cyanide species during the
process. It might be also a consequence of an eventual change
in the solubility conditions of the cyanide salts. The similarity
between the pH values of the solutions obtained from a given
precursor activated in Ar and in N2 under different conditions

500/3

Ar
N2

150/3

500/1

150/1

20

40

60

80

1035

4 8 ( 20 1 0 ) 1 0 3 210 3 7

100

-1
[CN ] (mg g )

Fig. 2 Cyanide formation in the course of the activation of

CUB-P using different KOH/precursor ratios and flow rates,
under N2 and Ar.

500/3

Ar
N2

150/3

150/1

10

20

-1

30

40

[CN ] (mg g )

Fig. 3 Cyanide formation in the course of the activation of

SB-P using different KOH/precursor ratios and flow rates,
under N2 and Ar.

(Table 3) rules out this possibility. Thus, the increment of the

cyanide concentration in the aqueous solutions measured at
higher flow rates or KOH/precursor ratios is most likely linked
to the completion of a chemical reaction involving the formation of cyanides during the activation. This increase in the
cyanide amount detected in these experiments is consistent
and must be related to a higher activation degree [13].
All the above results indicate that cyanides, ascribed to
structural nitrogen already present in the precursors, are
formed during the activation reaction, as XRD analysis of
the solids obtained after activation (i.e., before being washed)
confirms [19]. These cyanides are produced as a consequence
of the reducing atmosphere formed during the KOH carbon
activation process. Thus, when heating the carbon precursor/KOH mixture in an inert atmosphere, usually in the temperature range of 750850 C, carbon oxidation (carbon
conversion to potassium carbonate) takes place, together
with the formation of reducing products (metallic K and H2),
responsible of cyanide formation.
The cyanide concentrations reported by Robau-Sanchez
et al., when activating a lignocellulosic char in N2 (i.e., approx.
300 mg g1) [13], are two orders of magnitude higher than
those obtained for the QUE-P sample (Table 2, Fig. 1). Compositional differences between the two lignocellulosic chars under consideration (see Table 2 in [13] and Table 1 above)
cannot justify such a significant variation in the amount of
cyanides detected. A possible explanation is that they employed a stainless steel reactor (in the present work an alumina crucible) where the char/KOH mixtures were placed in
direct contact with the reactor wall. Fe has been traditionally
used as catalyst in the production of alkaline cyanides from
gaseous N2 [22,23]. The nitrogen mass balances of Table 3 excludes N2 fixation, within experimental error (DN = 0 1).
Fig. 4 shows a clear dependence of the amount of CN detected in the liquid phase on Ns,0 (see Table 3), for activations
carried out under the same experimental conditions (i.e.,
100 g of precursor, 1:1 KOH:precursor ratio) and 150 ml min
1
of Ar or N2. The trend depicted in Fig. 4 can be fairly accepted to be valid for precursors whose inorganic fraction
does not promote N2 fixation (a significant presence of transition metals, for example). Nevertheless, in that case, impor-

1036

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Table 3 Nitrogen mass balances of the activation process.

Precursor

Conditionsa

NS,0b

NS,fc

NLd

DNe

pH

QUE-P

N2/150/1
Ar/150/1
N2/150/1
Ar/150/1
N2/150/1
Ar/150/1
N2/150/3
Ar/150/3
N2/500/1
Ar/500/1
N2/500/3
Ar/500/3
N2/150/1
Ar/150/1
N2/150/3
Ar/150/3
N2/500/3
Ar/500/3
N2/150/1
Ar/150/1

0.8

0.6
0.7
2.0
2.4
2.1
1.9
1.0
0.8
1.5
1.2
0.5
0.4
1.0
1.0
0.8
0.8
0.5
0.5
1.6
1.4

0.18
0.10
6.91
6.52
3.91
3.93
4.40
4.65
4.13
4.57
4.85
5.24
1.51
1.52
1.57
1.67
1.99
1.85
0.96
1.26

0.0
0.0
0.0
0.0
0.0
0.3
0.6
0.6
0.4
0.3
0.6
0.4
0.1
0.1
0.2
0.1
0.4
0.2
0.5
0.4

13.08
12.99
12.83
12.82
12.78
12.78
12.49
12.45
12.75
12.76
12.59
12.60
13.09
13.07
13.02
12.95
13.07
13.07
12.79
12.81

CUA-P
CUB-P

SB-P

BIOS-P
a
b
c
d
e

8.9
6.0

2.6

3.1

Activation atmosphere/flow rate/KOH/precursor ratio.

Gram of N in 100 g of the precursor.
Gram of N in the washed, activated samples obtained from 100 g of the precursor.
Gram of N in the washing solutions (from total CN content) of activated samples obtained from 100 g of the precursor.
N balance: NS,0  (NS,f + NL).

14
12

CN (g)

10

N2
Ar
2
(R = 0.94)

4
2
0

10

NS,0 (g)

Fig. 4 Dependence of the amount of cyanides detected on

NS,0 (Table 3) during the activation of the different
precursors under the same experimental conditions (100 g
of precursor, 1:1 KOH:precursor ratio) and 150 ml min1 of
Ar or N2.

tant differences in the amount of cyanides formed under

nitrogen or argon should be expected.

4.

Conclusions

Soluble cyanide is formed during the alkaline activation of

nitrogen-containing chars as a consequence of structural
nitrogen present in the precursor. The amount of cyanides obtained when the activation is carried out under nitrogen or argon atmospheres is essentially the same, as far as iron or

other cyanide formation promoters are absent from the reaction chamber. Increasing the flow rate or KOH/precursor ratio
tends to raise the amount of cyanides formed. A correlation
between the cyanides detected in solution and the nitrogen
content of the precursors could be established. Cyanide formation during chemical activation with hydroxides can be
minimised by reducing the N content of the precursor. Finally,
attention should be paid to the KOH activation process of
some carbon precursors because high cyanide concentrations
(e.g., as high as 130 mg of CN per gram of precursor) can be
eventually reached for chars with relatively high N contents
(e.g., 9 wt.%, dry basis). This remarks that materials with
low nitrogen content should be selected, from an environmental point of view, to be used as precursors for the preparation of activated carbons by KOH activation.

Acknowledgements
This work was funded by MEC and MICINN (CTM2005-07524C02-00, CTM2008-06869-C02-00/PPQ and PRT2007-0421
projects).

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