Proceedings of the International Conference on Circuits, Systems, Signals
Replacement of gas phase with liquid, for
hexamine production
Anita Kovač Kralj¹ Davorin Kralj²
Faculty of Chemistry and Chemical Engineering, University of Maribor,Smetanova 17, Maribor, Slovenia
¹Art-K BusinessConsulting, Na gricu 47, 2000 Maribor ²
anita.kovac@uni-mb.si, davorin.kralj@amis.net
Abstract: Chemical kinetics, also known as
reaction kinetics, is the study of chemical processes’ rates.
Chemical kinetics includes investigations into how different
experimental conditions can influence the speed of a
chemical reaction, and yield information about the reaction's
mechanism and transitional states, as well as the
construction of mathematical models that can describe the
characteristics of a chemical reaction. The physical state
(solid, liquid, or gas) of a reactant is also an important factor
regarding rate of change. Many syntheses carried out during
the gas-phase, providing a synthesis of the same product,
can also be performed during the liquid phase, for
simplicity, for major opportunities regarding analysis, and
lower risk. This paper studies the kinetic determination of
hexamine production in an aqueous solution of ammonia
hydroxide and formaldehyde. In the literature, a lot of
information can be found about the kinetic determination of
hexamine production during gaseous phases. Hexamine
(C6H12N4) was produced from aqueous ammonia hydroxide
(NH4OH) and aqueous formaldehyde (CH2O) in a batch
reactor at different temperatures (T1 = 23 ºC, T2 = 24 ºC, T3
= 26 ºC and T3 = 28 ºC): 6 CH2O + 4 NH4OH = C6H12N4 +
10 H2O. The reaction was observed by measuring a certain
concentration by titration, in our case, non-reactive
ammonia hydroxide. The concentration and kinetic
parameters of the ammonia hydroxide’s reaction (reaction
rate constant, rate order, activation energy) were determined
by using experimental parameters.
Keywords – production of hexamine, concentration, kinetics,
titration, reaction rate constant, rate order
I. INTRODUCTION
Chemical kinetics deals with the experimental
determination of reaction rates from which rate laws and
rate constants are derived [4]. Relatively simple rate laws
exist for zero order reactions (for which reaction rates are
independent of concentration), first order reactions, and
second order reactions, and can be derived at for others. In
consecutive reactions the rate-determining step often
determines the kinetics. In consecutive first order reactions,
158
a steady state approximation can simplify the rate law. The
activation energy for a reaction is experimentally
determined through the Arrhenius and Eyring equations.
The main factors that influence the reaction rate include: the
physical states of the reactants, the concentrations of the
reactants, the temperature at which the reaction occurs, and
whether or not any catalysts are present during the reaction.
The physical state (solid, liquid, or gas) of a
reactant is also an important factor regarding the rate of
change. When reactants are in the same phase, as in aqueous
solution, thermal motion brings them into contact. However,
when they are in different phases, the reaction is limited to
the interface between the reactants. Reaction can only occur
at their area of contact and, in the case of a liquid and a gas,
at the surface of the liquid. Vigorous shaking and stirring
may be needed to bring the reaction to completion. This
means that the more finely divided a solid or liquid reactant,
the greater its surface area per unit volume, and the more
contact it makes with the other reactant’s, the faster the
reaction.
An aqueous solution is a solution in which the
solvent is water. It is usually shown in chemical equations
by appending (aq) to the relevant formula. The word
aqueous means pertaining to, related to, similar to, or
dissolved in water. As water is an excellent solvent, as well
as naturally abundant, it has logically become a ubiquitous
solvent in chemistry.
In 1864, Peter Waage pioneered the development
of chemical kinetics by formulating the law of mass action,
which states that the rate of a chemical reaction is
proportional to the amounts of reacting substances.
Hexamine or hexamethylenetetramine is used in
pharmaceutical industries as a primary feed material, and in
chemical industries as an intermediate material. It is highly
soluble in water and, like some other tertiary amines, has an
inverse solubility at low temperatures [1].
An optimum method for producing hexamine from
formaldehyde and gaseous ammonia is the Meissner
process, in which the reaction and crystallization stages take
place simultaneously to produce crystalline hexamine. Due
to a high dissolution rate of ammonia and formaldehyde in
the aqueous solution and a high reaction rate during
 Proceedings of the International Conference on Circuits, Systems, Signals
hexamine production, the crystallization stage controls the
Meissner process [2].
The values for kinetic parameters regarding
hexamine crystallization from aqueous solution, necessary
for controlling industrial crystallizers, were calculated by
Alamdari and Tabkhi [6].
Many syntheses carried out during the gas-phase,
provided a synthesis of the same product can also be
performed during the liquid phase, for simplicity, for major
opportunities regarding analysis, and lower risk. This paper
studies the kinetic determination of hexamine production, by
titration of an aqueous solution of ammonia hydroxide and
formaldehyde with reaction:
6 CH2O + 4 NH4OH = C6H12N4 + 10 H2O
In the literature, a lot of information can be found about the
kinetic determination of hexamine production during
gaseous phases:
6 CH2O + 4 NH3 = C6H12N4 + 6 H2O
I REACTION RATE
For a constant-volume batch reactor [3], the rate at
which reactant A’s appears (ammonia hydroxide), rA, is
given by:
dc A
− rA = (1)
dt
where rA can be expressed as:
− rA = k ⋅ c An ⋅ cBm (2)
where k is the reaction rate constant, n and m are the
reaction orders with respect to species A (ammonia
hydroxide) and B (formaldehyde), respectively. Since
formaldehyde is in excess, c B remains essentially
unchanged during the course of the reaction:
− rA = k '⋅c An (3)
where k' is a pseudo rate constant
k ' = k ⋅ c Bm ≈ k ⋅ cB 0 (4)
The reaction order and rate constant can be
determined by the integral analysis method. In this method,
the rate expression is guessed and the differential equation
used to model the batch system is integrated. If the assumed
order is correct, the appropriate plot (determined from the
integration) of concentration-time data should be linear.
For the first-order case where – rA = k cA, the integration of
equation 3.1 yields:
c A0
k ⋅ t = ln (5)
cA
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where cA is ammonia hydroxide concentration and cA0 is the
initial ammonia hydroxide concentration.
For the second-order case where – rA = k cA2, the integration
of equation 3.1 yields:
1 1
= + k ⋅t (6)
c A c A0
The specific reaction rate, k, is a function of reaction
temperature and is given by the Arrhenius equation:
Ea
k = k 0 ⋅ e − R⋅T (7)
where k0 is a pre-exponential factor, Ea is the activation
energy for the reaction, and T is the absolute temperature.
II CASE STUDY
Hexamine, also called hexamethylenetetramine or
methenamine (INN), is a heterocyclic organic compound
that can be prepared by the reaction of formaldehyde and
ammonia [5]. It is crystalline and white in appearance.
Particle sizes range from 80-800 micrometres. It is
moderately soluble in water and very soluble in most
organic solvents. It has a cage-like structure similar to
adamantane.
It has two very different types of usage: as an
antibiotic (commonly hippurate salt, methenamine
hippurate), and as a solid fuel tablet used for cooking while
camping or hiking. The name methenamine is more
common regarding its medicinal uses and hexamine is more
common in commercial uses. Methenamine hippurate is
mainly used for the prophylaxis (prevention) of urinary tract
infections, where it is hydrolysed in the acidic pH of the
urine to form formaldehyde. Formaldehyde is an effective
antiseptic against bacteria and fungi in vitro, but may be
ineffective in vivo - it has been shown to be ineffective for
the treatment of urinary tract infections. Furthermore,
certain bacteria (including Proteus and Pseudomonas)
increase urinary pH, rendering methenamine ineffective. In
China, a 10% solution is used as a deodorant.
As a food additive, hexamine is used as a
preservative in cheeses. It has E number E239 but in some
countries is banned for this use.
Hexamine can be absorbed through the skin, and
some people are allergic to it. This is normally manifested as
a rash.
Hexamine is used as a component with 1,3,5-
trioxane in hexamine fuel tablets (often called Esbit). This
solid fuel in tablet form is used by campers, the military and
relief organizations for heating camping food or military
rations. It is smoke-free, has a high energy density, does not
liquefy while burning, and leaves no ashes.
Another important area for the use of hexamine is
in the production of powdery or liquid phenolic resin
 Proceedings of the International Conference on Circuits, Systems, Signals

preparations and phenolic resin moulding compounds, The degree of conversion, XA, is:
where hexamine is added as a hardening component. These c A0 − c A
products are used as binders, e.g. in brake and clutch linings, XA = (11)
abrasive products, non-woven textiles, formed parts c A0
produced by moulding processes, and fireproof materials.
It is used in rubber and textile adhesives, in paints The initial ammonia hydroxide concentration, cA0 was
and lacquers, in the photographic industry, in the production analysed by the first measurement (Number 1; Table 1).
of explosives such as RDX, as a corrosion inhibitor, as a Figure 2 illustrates the plot of cA as a function of time at
protein modifier, as a reagent in chemical analysis, and in different temperatures.
the production of deodorants and hair fixers, among many
other uses.

III EXPERIMENT

A schematic diagram of the laboratory apparatus is

shown in Figure 1. A batch reactor with a stirrer was used in
the experiment. Ammonia hydroxide (2.15 mL 25 %) was
dissolved in water (0.35 L) and heated into a reactor at
different temperatures (T1 = 23 ºC, T2 = 24 ºC, T3 = 26 ºC
and T3 = 28 ºC). Surplus formaldehyde (4 mL 36.5 %) was
added:
6 CH2O + 4 NH4OH = C6H12N4 + 10 H2O
B A
stirrer
Figure 2: Concentration of ammonia hydroxide, cA, as a function of time at
different temperatures.

Figure 3 presents the plot of conversion degree, XA, as a

function of time at different temperatures.
reactor

solution

Figure 1: The apparatus – stirred batch reactor.

Both substances were mixed. The concentration of non-

reactive ammonia hydroxide, cA was analysed by using a
titration analytical method depends on time (Table 1). 10
mL 0.1 mol/L HCl was added to the 10 mL sample, which
stopped the reaction (reaction 1), and retitration took place
with 0.1 mol/L NaOH (reaction 2):

molHCl = molNaOH + molsample (8) Figure 3: The plot of conversion degree XA, as a function of time at
different temperatures

(c ⋅ V )HCl = (c ⋅ V )NaOH + (c ⋅ V ) A (9)

10 · 0.1 = 0.1 · VNaOH + 10 · cA,
NH4OH + HCl → NH4+ + Cl– + H2O
+
NaOH + HCl → Na + Cl + H2O
(10) The plot of ln(cA0/cA) as a function of time is non-linear. As
Figure 5 illustrates (Table 2), the plot of (1/cA) as a function
of time is linear, which suggests that the rate law is second
order with respect to ammonia hydroxide concentration
(reaction 1) under given reaction conditions for excess formaldehyde.
–
(reaction 2) The slope represents the rate constant, k. The rate constant
was found to be 1.327 L/(mol min−1) at 23 oC. The data
show the reaction is second order at all temperatures studied

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 Proceedings of the International Conference on Circuits, Systems, Signals

(Table 3). The initial parameters deviated from the linear 2 5.59 7.0 0.030 33.3333 0.5714
plot because of the non-homogeneous solution. 3 7.03 7.1 0.029 34.4828 0.5857
4 9.10 7.4 0.026 38.4615 0.6286
Table 1: The experimental data and calculation at T= 23 °C.
5 10.15 7.5 0.025 40.0000 0.6429
Nu. 6 11.21 7.5 0.025 40.0000 0.6429
t/min VNaOH/ml cA/(mol/L) ln(cA0/cA)
7 12.35 7.6 0.024 41.6667 0.6571
1 0.00 3.00 0.070 0.000 8 15.40 7.7 0.023 43.4783 0.6714
9 17.09 7.7 0.023 43.4783 0.6714
2 5.59 7.00 0.030 0.847 10 18.16 7.7 0.023 43.4783 0.6714
11 19.34 7.8 0.022 45.4545 0.6857
3 7.03 7.10 0.029 0.881

4 9.10 7.40 0.026 0.990

5 10.15 7.50 0.025 1.030

6 11.21 7.50 0.025 1.030

7 12.35 7.60 0.024 1.070

8 15.40 7.70 0.023 1.113

9 17.09 7.70 0.023 1.113

10 18.16 7.70 0.023 1.113

11 19.34 7.80 0.022 1.157

Figure 5: The plot of (1/cA) as a function of time at 23 ºC.

Table3: The reaction rate constant, k:

T/ºC k/ L/(mol min−1)

23 1.327

24 1.331

26 1.420

28 1.632

The experiment at temperatures 24 ºC, 26 ºC and 28 ºC was

Figure 4: The plot of ln(cA0/cA) as a function of time at 23 repeated using the same procedure.
ºC.

Table 2: The experimental data and calculation at T= 23 °C. Taking the logarithm of the Arrhenius equation (7):
Zap. Ea
št
t/min VNaOH/ml CA/(mol/L) (1/CA)/(L/mol) XA ln k = ln k0 − (12)
R ⋅T
1 0.00 3.0 0.070 14.2857 0.0000

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 Proceedings of the International Conference on Circuits, Systems, Signals

72,3
the plot of ln(k) and 1/T should be a straight line and the 70 HEKSAMIN - standard
slope is proportional to the activation energy (Table 4). The
65
activation energy is 32.23 kJ/mol (Fig. 6).
60
Table 4: The data for determining activation energy.
55

T/°C T/K (1/T)/K-1 k/(L/mol min) lnk 50

1938,31 1592,04
1828,12
2146,30
23 296 0.00338 1.327 0.2829 45 1784,55

24 297 0.00337 1.347 0.2979 %T

40
2016,50
1746,34
833,87

1487,04
26 299 0.00334 1.420 0.3507 3324,87
35 3462,29
28 301 0.00332 1.657 0.5050
30

25

20
1439,41

15
2871,53 1456,36
1370,61
11,6 1238,99 1001,22 811,40 673,14 512,84
4000,0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0
cm-1

Figure 7: The peaks from the standard’s hexamine.

74,3

70 HEKSAMIN - vzorec

65

60

55 1784,49 1592,05 833,41

2016,39 1746,25
1487,01
50

45 3461,99

40
%T
35
1439,25

30

25
Figure 6: The plot of ln k and 1/T.
20
2920,24 1048,06
2952,69 1456,68
15 2871,05
1370,13
The slope of the graph is: 10
512,46

811,50671,29
1237,26 1004,90
3,7
−Ea/R = 3877 K (13) 4000,0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400,0
cm-1

E a = 3877 K ⋅ 8.314J/(mol K) = 32.233 kJ/mol (14) Figure 8: The peaks from the sample’s hexamine.

This reaction took place at room temperature, thus

confirming the activation energy value, which was low.
The peaks from the standard’s and sample’s hexamine
(Figures 7 and 8) were analysed using infrared spectroscopy.
The important peaks were the same, thus confirming that
hexamine was produced.
IV. CONCLUSION
Many syntheses carried out during the gas-phase,
providing a synthesis of the same product can also be
performed during the liquid phase, for simplicity, for major
opportunities for analysis, and lower risk. This paper studies
the kinetic determination of hexamine production in an
aqueous solution of ammonia hydroxide and formaldehyde.
In the literature, a lot of information can be found about the
kinetic determination of hexamine production during
gaseous phases. We determined the concentration and

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 Proceedings of the International Conference on Circuits, Systems, Signals

kinetics of ammonia hydroxide to hexamine by measuring

the concentration using titration - ammonia hydroxide in a
batch reactor. The ammonia hydroxide reacts as a second-
order reaction. The rate constant was found to be 1.327
L/(mol min−1) at 23 ºC. The hexamine can be produced from
an aqueous solution of ammonia hydroxide and
formaldehyde with a high-degree of conversion under low
temperatures. The activation energy was 32.23 kJ/mol. The
same peaks for the standard’s and sample’s hexamine
confirms that hexamine was produced.

REFERENCES

[1] Smolin E.M. and Rapoport L., The chemistry of heterocyclic

compounds, S-Triazines and derivatives, Interscience publication, New
York , (1959).
[2] Meissner F., Schwiedessen E and Othmer D.F. Shatyski, Continuous
production of hexamethylenetetramine, Ind. Eng. Chem. 46 (1954)
724.
[3] Haji S. and Erkey C., Kinetics of hydrolisis of acetic anhydride by in
situ FTIR spectroscopy, Chemical Engineering Education, (2005)
56−61.
[4] http://en.wikipedia.org/ chemical kinetics
[5] http://en.wikipedia.org/ hexamine
[6] Alamdari A. and Tabkhi F, Kinetics of hexamine crystallization in
industrial scale, Chem. Eng. And Processing 43 (2004) 803−810.

163