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International Journal of Geosciences, 2011, 2, 227-230

doi:10.4236/ijg.2011.23024 Published Online August 2011 (http://www.SciRP.org/journal/ijg)

Calculation of Standard Thermodynamic Potentials for


Na-Zeolites with the Use of Linear Programming Problems

Oleg Viacheslavovich Yeriomin


Establishment of the Russian Academy of Sciences, Institute of Natural Resources, Ecology, and
Cryology,
The Siberian Branch of the Russian Academy of Sciences, Chita, Russian
Federation
E-mail:
yeroleg@yandex.ru
Received April 1, 2011; revised June 2, 2011; accepted July 6,
2011

Abstract

Linear programming problems for Na-Al-Si-O-H system have been formulated and solved for calculations of
standard enthalpies and Gibbs potentials of zeolites with unknown thermodynamic properties. The calcula-
tions are based on dual solutions of linear programming problems. Comparison of numerical results with
published data gives relative mistakes of estimations less than one percent. On the basis of calculated poten-
tials the standard entropies have been estimated. The standard thermodynamic potentials for eight natural
zeolites with unknown properties have been calculated. The presented method does not demand any infor-
mation about crystal structure of zeolites and can be applied to any of their stoichiometric presentation.

Keywords: Na-Zeolites, Standard Thermodynamic Potentials, Linear Programming


1. Introduction Sedangkan zeolit alami dan disintesis sering
disajikan oleh variabel stoikiometri senyawa peran
Zeolit adalah mikroporous aluminosilikat metode empiris perhitungan termodinamika mereka
yang sangat penting zat penggunaan sifat namic sangat penting.
multiguna. Memiliki spesifik kerangka kerja mereka Metode pemodelan termodinamika dalam
secara aktif berpartisipasi dalam proses sorp-dan geochemis-
pertukaran ion, katalisis, yang menyebabkan mereka coba izinkan untuk menganalisis sifat fisik dan kimia
aplikasi luas dalam industri, pertanian, kedokteran, sistem dan komponen atas dasar teorema ganda
proteksi lingkungan. dalam pemrograman cembung [3]. Dengan
Pengetahuan tentang sifat termodinamika menggunakan prolin linear
zeo-lites menyediakan investigasi perilaku mereka di masalah gramming untuk tembaga sulfat kompleks
alam, teknologi dan proses biokimia, secara kesalahan relatif dari perhitungan potensi Gibbs
bersamaan tesis material baru. standar
Bersamaan dengan metode eksperimental telah diperoleh sekitar 1% [4]. Kami akan
penentuan Ada sifat fisik-kimia zeolite beberapa mempertimbangkan
metode prediksi sekarang tersedia. Satu kelompok penerapan metode pemrograman linier untuk suatu
metode didasarkan pada aditivitas oksida (atau mation dari potensi termodinamika untuk Na-zeolit.
hidroksidaides) komponen zeolit [1]. Model-model
ini memiliki akurasi yang baik untuk bentuk anhidrat 2. Methodology
tetapi dalam kasus dengan air zeolitik perbedaan
estimasi lebih signifikan penting. Kelompok metode For five chemical elements Na-Al-Si-O-H we’ll
con-
lain menggunakan framework data zeolit [2].
thesis of new materials. struct the set from six substances including
S zeolites

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Alongside with experimental methods of in such a way that stoichiometric A has a full
determina- matrix
tion of physical-chemical properties of zeolites rank. Then for it is possible to write down the
there are S unique
some predictive methods now available. One group chemical reaction [5]. For example, for
of methods is based on the additivity of oxides (or S = {NaAlSi2O6·H2O (analcime); NaAlSi2O6
hydrox- ides) components of zeolites [1]. These (dehy- drated analcime); Na2Al2Si3O10·H2O
models have a (natrolite); NaAl-
good accuracy for anhydrous forms but in cases SiO4 NaAl3Si3 O10 (paragonite) O2 }
with (nefeline); (OH) 2 ;
zeolitic water the divergence of estimations is more reaction can be
sig- written:
Na Al Si 2H O
nificant. Another group of methods uses the NaAlSi O
framework O
data of zeolites [2]. 2 6 2 2
3 10 2 (1)
Whereas natural and synthesized zeolites are 2NaAlSi 2 O6 H 2 O
often NaAlSiO4
presented by stoichiometry variable compounds the Let’s define a following linear programming
role of empirical methods of calculation of their problem:
thermody- namic properties is very important.
min f H x, Ax b, x 0,
(2)
Methods of thermodynamic modelling in where H —values of standard enthalpy
geochemis-
try allow to analyze the physical and chemical formation
f
properties from elements for substances from S ,

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228 O. V. YERIOMIN

x - vector of their quantity, data consistency equation of “Selektor” software


b - vector of chemical elements mass [3] for calculation of S :
balance. 
If x is a nonsingular solution of (2), f

then: S f G T L,
H (7)
Hf x by ,
(3) where T - temperature (298.15 L Y z
K), s ,
where y —solution of equivalent to (2) dual s , s , s , s , s ) = (51.2, 28.3, 18.8,
problem (s Na102.5,Al65.0)
Si
[6]: O H s - entropies of chemical
J/mole/K. Values ele-
of
max by, A y 
, ments are taken from [8].
Results of calculations on (6) and (7) and
where fH (4)
comparison with published data [7] are presented in
' - index of transposing. Table 1.
If x contains nonzero quantity of any zeolite

xz 0 , then from (3) 3. Results and Discussion


follows:

fH z A z y , The set S defines the forms of problems (2). The
(5) choice
where f  z —the potential of at of components S is rather arbitrary. It is desirable
H zeolite z equi- that the
librium A z —vector-column of A matrix, included zeolites have experimental or estimated
, corre- ther-
sponding to stoichiometric formula of zeolite z . modynamic data. The condition of full rank A
Equality (5), namely the y value can be matrix
used for allows to make the preliminary chemical
interpretation of

calculation of f z for Na-zeolites system. The problem (2) for Gibbs energy can be
unknown means a H by con- sidered as thermodynamic equilibrium
formula: calculation for the
heterogeneous
and mixture S under standard temperature
fH z Y z,
pressure. The solutions of (2) define zeolites for
y (6) which
where Y z —stoichiometric vector of the condition (5) will be satisfied. They can be
zeolite z . named
Let’s consider a numerical “basic” zeolites - on the basis of which the
example. estimation on
The f values for component according (6) will be applied for other substances. Natrolite
H S to and
their written sequence are taken from dehydrated analcime are the “basic” zeolites in our
[7]: cal-
f = – (3291100, 2974800, 5718600, culations. We can see from Table 1 the
H 2073800, implementation
5943500, 0) J/mole. mole – mole of dehydrated analcime and mole of
Vector of mass balance is defined by reaction (1): natro- lite.
b (bNa , bAl , bSi , bO , bH ) (3, 3, 5, 18, 4) The problem (4) has solution:
mole.
The problem (2) has solution: x = (0, 1, 1, 0,
0, 0)
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of an optimality criterion (5) - exact equality of by means (6) is simple and represents the scalar
thermo- multiplica- tion of two vectors. For any
dynamic potentials for “basic” zeolites.
stoichiometric forms of zeo- lites the use of (6)
For the existing solution y* the calculation of un-
gives the molal dimension of poten-
known enthalpies (or Gibbs energies) of substances
y * , y* , y * , y* , y* (32157, –380213, – tials. As a example, the estimations on (6) and
(y Na) Al Si 26705, compari-
O H son with calorimetry measurements [10] for some
–428889, 51073)
J/mole. hy- drous and anhydrous forms of sodalite family
The equation (6) for dachiardite can be zeolites are presented in Table 2.
written: The calculated on (6) and (7) thermodynamic
poten- tials for some natural Na-zeolites [11] with
f H (Na
4 4Al20Si 48 O 2 13H O) unknown properties are presented in Table 3. These
Y(Na4 Al 4 Si O
20 48 13H
2 O)y data may be used in geochemical calculations of
processes with their participation.
(4, 4, 20, 61, 26)
The vector y* can be considered as the chemical
(32157, 380213, 26705, 428889, ele-
51073)
= 26760655 (J/mole).

Similarly we’ll evaluate f values in (2). ments contributions to potentials of zeolites.
the data [7]: G For The en- thalpy solution of (2)—y* are presented as
a bar diagram
f = – (3291100, 2974800, 5718600, on Figure 1. We can see from figure that oxygen
G 2073800, and
5943500, 0) J/mole, aluminium atoms provide the most contributions in
solution (2): x = (0, 1, 1, 0, 0, 0) en-
mole, thalpy potentials. Hydrogen and sodium have a
positive
solution y * , y** , y* , y* , (19309 energy values.
(4): (y Nay ) Al Si ,
O H The stability of calculations on (6) depends on
–358452, –29039, –401930, 67990) J/mole.
Gibbs potentials and enthalpies are connected vari- ability of y* components in connection with
with data uncer-
standard S . We’ll use the tainty for “basic” zeolites. This problem demands
entropies thermodynamic the

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O. V. YERIOMIN 229

Table 1. Values of standard thermodynamic potentials for some Na-zeolites calculated on (6) and (7).
In brackets - a relative mistakes of calculations (%) with published data [7,9].
[7] Calculated on
(6) and (7)
 f G   f H   f G   f H 
    
Chemical formula (mineral) S S 
(kJ/mole) ( kJ/mole) (J/mole/K) ( kJ/mole) (kJ/mole) (J/mole/K)
2808.8 2974.8 174.5
NaAlSi2O (dehydrated
6 analcime) 2808.8 2974.8 175.4
(0) (0) (0.5)
5316.6 5718.6 356.9
Na2Al2Si3O10·H2O (natrolite) 5316.6 5718.6 359.7
(0) (0) (1.0)
3074.7 3301.5 210.3
NaAlSi2O6·H2O (analcime) 3068.3 3291.1 234.3
(0.2) (0.3) (11.4)
24687.3 26760.6 1919
Na4Al4Si20O48·3H2O (dachiardite) [9] 24724.0 26723.0 1947 (0.1) (0.1) (1.5)

Table 2. The standard enthalpies of formation f (kJ/mole) of some hydrous and anhydrous
from elements H forms of
sodalite family materials [10]. In brackets—mistakes of calculations on (6).
Chemical f kJ/mole Calculated on (6)
formula H
N
Na
a7.82 7.82(OH)
(OH) 1.84[Al
1.84 [Al
5.98 6.02Si
Si5.98 O6.02 O242O)
24](H ] 3.27 13181.7
14275.4 13171.5
14239.9 (0.1)
(0.2)
Na7.60(OH)1.64[Al5.96Si6.04O24](H2O)3.00 14093.2 14076.2 (0.1)
Na7.60(OH)1.64[Al5.96Si6.04O24] 13085.1 13095.9 (0.1)

Table 3. The standard thermodynamic potentials of some natural Na-zeolites calculated on (6,7).
Chemical formula G , H , f
S , J/mole/K f
(mineral) kJ/mole kJ/mole

Na8Al8Si16O48·22H2O 28321 30947 2120.


Na8Al 6Si6O24(OH)2·3H2O 13282 14170 1205.
(gmelinite)
NaAlSi5O12·3H2O (mordenite) .3
6105. .0
6649. 6
449.
(cancrinite) .5 .7 8
Na2Al2Si3O10·3H2O 3
5582. 6
6037. 8
390.
(paranatrolite)
Na8Al6Si6O24(OH)2 (sodalite) 5
12484 9
13212 3
908.
Na5Al5Si11O32·1H2O .7
17802 .7
19364. 7
1298.
Na(gobbinsite)
1.6Al1.5Si36O72·18H2O .3
35278 2
38653 4
2788.
(heulandite)
NaAlSi3O8·3.5H2O (zeolite) .2
4572. .1
5008. 2
348.
5 4 4

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Figure 1. The enthalpy potentials of chemical elements for Na-zeolites.

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23 O. V. YERIOMIN
0

supplementary analysis. For our example, the chemistry: The Theory, Algorithms,
handbook [7] contains one enthalpy value for Software, Exam- ples,” in Russian,
Publishing house GEO, Novosibirsk,
natrolite, and differ- ence between maximum and 2010, p. 287.
minimum values for dehy- drated analcime is 15.4 [4] O. V. Yeriomin, S. V. Vinnichenko and G. A.
kJ/mole (~0.6%). For this un- certainty the Yurgenson, “Evaluation of Standard Gibbs
divergence of estimations on (6) for all con- sidered Potentials for Copper Hy- droxosulfate
in article substances does not exceed 1%. Hydrates from Solutions of Dual Linear Pro-
Evaluation on (6) gives for all Na-zeolites gramming Problems,” in Russian, Doklady
enthalpy value of zeolitic water equal to –326.7 Akademii Nauk, Vol. 409, No. 3, 2006, pp.
kJ/mole. This energy of water is more preferable 386-388.
that ones in structure of ice-I –292.7 kJ/mole [12]. [5] N. F. Stepanov, M. Y. Yerlukina and G. G.
The considered method has restriction in the Fillipov, “The Methods of Linear Algebra in
applica- bility only to Na-zeolites, but can be Physical Chemistry,” in Russian, Publishing
extended by addi- tion in system of calcium, Moscow State University, Moscow,
magnesium and (or) others chemical elements. 1976, p. 360 .
[6] V. I. Shmuriov, “Introduction in Mathematical
4. Conclusions Program- ming,” in Russian, Institute of
Computer Researches, Moscow, 2002, p. 192.
[7] T. L. Wood and R. M. Garrels,
“Thermodynamic Values at Low Temperature
for Natural Inorganic Materials,” Oxford
University Press, Oxford, 1987, p. 265.
The method calculation standard [8] A. A. Ravdel and A. M. Ponomariova, “The
of thermodynamic Brief Hand-
po- tentials for Na-zeolites has been proposed book of Physico-chemical Data,” in Russian,
Khimiya,
on the basis of dual solutions of linear Leningrad, 1983, p. 232.
programming problems. The re- sults of estimation
[9] L. P. Ogorodova, L. V. Melchakova and I. A.
have acceptable accuracy with pub- lished
Kiseleva, “A Study of Dachiardite, a Natural
experimental and predicted data. The pre- sented
Zeolite of the Mor- denite Group,” in Russian,
method does not demand any information about
Zhurnal Fizicheskoy Khimii, Vol. 81, No. 11,
crystal structure of zeolites and can be applied to 2007, pp. 1953-1955.
any of their stoichiometric presentation.
[10] E. C. Moloy, Q. Liu and A. Navrotsky,
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[11] V. V. Bakakin and Yu. V. Seryotkin,
doi:10.1007/s10934-007-9105-7
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