Arabian Journal of Chemistry (2017) xxx, xxx–xxx

King Saud University

Arabian Journal of Chemistry

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Optimization and modeling of synthesis parameters

of neodymium(III) bromide by dry method using full
factorial design analysis
Yassine Bounouri a, Madjid Berkani a,*, Abdelmalek Zamouche a, Leszek Rycerz b

a
Laboratoire de Physico-chimie des Mate´riaux et Catalyse, Faculte´ des Sciences Exactes, Universite´ de Bejaia, Targa
ouzemmour 06000, Algeria
b
Chemical Metallurgy Group, Department of Chemistry, Wroclaw University of Technology, Wybrzeze Wyspianskiego 27,
50-370 Wroclaw, Poland

Received 19 January 2017; accepted 6 May 2017

KEYWORDS Abstract The synthesis of neodymium(III) bromide (NdBr3) by sintering brominating of neody-
Neodymium(III) bromide; mium oxide (Nd2O3) with ammonium bromide (NH4Br) was investigated. The influence of various
Lanthanide halides; synthesis parameters (temperature, contact time and stoichiometry) on the reaction yield was stud-
Reaction yield; ied and optimized. The main interaction effects of the synthesis parameters on the reaction yield
Full factorial design were also determined by a full 23 factorial designs with six replicates at the center point.
This study showed that the optimum conditions for the synthesis of NdBr3 are following: contact
time t = 60 min, stoichiometry in moles Nd2O3:NH4Br = 1:24 and temperature T = 400 °C. The
reaction yield for these parameters was equal to 97.80%. The first order model was obtained to pre-
dict the reaction yield as a function of these three parameters. It was shown that all parameters have
a significant positive influence on reaction yield. In addition it was pointed out also that the inter-
action effects between them are significant.
Ó 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

* Corresponding author.
E-mail address: berkanima@yahoo.fr (M. Berkani).
Peer review under responsibility of King Saud University.

Production and hosting by Elsevier

http://dx.doi.org/10.1016/j.arabjc.2017.05.003
1878-5352 Ó 2017 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: Bounouri, Y. et al., Optimization and modeling of synthesis parameters of neodymium(III) bromide by dry method using full fac-
torial design analysis. Arabian Journal of Chemistry (2017), http://dx.doi.org/10.1016/j.arabjc.2017.05.003
2 Y. Bounouri et al.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Experimental. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. Full factorial designs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.1. Thermodynamic aspect of the reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.2. Thermal analysis of reagents by TG–DTG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.3. Optimization of the synthesis parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.3.1. Influence of the contact time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.3.2. Influence of the stoichiometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.3.3. Influence of the temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.4. Factorial design analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.4.1. Statistical analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.4.2. Variance analysis (ANOVA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.4.3. Correlation coefficients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.4.4. Residual analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.5. Main and interaction effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

1. Introduction to determine a mathematical model connecting these three factors with

In the past 50 years, lanthanide halides were the subject of several stud-
ies. The majority of these studies were focused on their chemical and
physical properties. The physicochemical properties of the compounds
they form, for instance with the alkali halides, can be examined and
correlated in a way which is unique since the lanthanides regularly vary
along the series they form in the periodic table. This is due to the pres-
ence of f electrons in the lanthanide ions, which do not participate in
the formation of the chemical bonding (Gschneidner et al., 2003).
These compounds are used in various fields such as: reprocessing of
nuclear wastes (Kobayashi et al., 1998), recycling of spent nuclear fuel
(Ogawa et al., 1995; Ogawa and Igarashi, 1998), catalysis and chemical
synthesis (Doty et al., 2007), medical imaging (Beckert et al., 2016),
and in the lighting industry (Muklejohn et al., 1993; Markus et al.,
2005). These different applications require knowledge of their physic-
ochemical, structural and thermodynamic properties. The study of
these properties requires high purity of these salts in order to have
accurate data (Rycerz and Gaune-Escard, 2008; Kolodziej et al.,
2009; Chojnacka et al., 2014). These anhydrous salts that are commer-
cially available still contain small amounts of water and cannot be used
for such a study. Therefore, good control of the different stages of syn-
thesis and optimization of parameters that can affect the synthesis
reaction is the preliminary step to cross (Gaune-Escard et al., 1994;
Peringer et al., 2008; Mendil et al., 2013). The determination of these
optimum conditions requires a large number of experiments and takes
a lot of time. These drawbacks can be avoided by applying the exper-
imental design method, which allows studying the effects of several fac-
tors on one or more responses, and to find a mathematical model that
connects the response to the factors (Kincl et al., 2005). This method
has several advantages such as: providing maximum information with
minimum experiments, the possibility of increasing the number of fac-
tors studied or their levels, taking into account possible interactions
between factors, simple modeling results and a good search of the opti-
mal response (Lazic, 2006; Tinsson, 2010). The aims of the present
work were as follows: firstly, optimization of synthesis parameters
(temperature, contact time and molar ratio neodymium oxide: ammo-
nium bromide) of neodymium(III) bromide (NdBr3) by sintering
brominating of neodymium oxide (Nd2O3) with ammonium bromide
(NH4Br), secondly, application of a 23 full factorial design in order
reaction yield and to gain insight into how the various factors interact
and influence the response.
2. Experimental
NdBr3 was synthesized from neodymium oxide Nd2O3 (Sigma-
Aldrich, 99.9%) by sintering brominating with NH4Br (Sigma-
Aldrich, 99%). A mixture of Nd2O3 and NH4Br in well-
defined proportions was ground and homogenized in a mortar,
and placed into alumina crucible. Then, the crucible was
inserted into a quartz reactor and placed in an electric furnace.
The furnace temperature was controlled by the programmer
EUROTHERM 2404. This resulted in a process where volatile
products were absorbed in a scrubber filled with sodium
hydroxide. The entire experiments were carried out in an argon
atmosphere. The yield of the reaction was determined by
chemical analysis. Neodymium(III) bromide is soluble in water
whereas unreacted neodymium oxide is water insoluble. Thus
dissolution of the reaction product transfers neodymium bro-
mide into solution, whereas neodymium oxide stays in insol-
uble solid residue. The resulting product of the reaction was
cooled down, and then dissolved in 150 cm3 of 0.05 M HCl
solution using magnetic stirrer for 10 min. In this step obtained
neodymium(III) bromide was transferred to the solution. The
solution of 0.05 M HCl was used to prevent hydrolysis of neo-
dymium ions formed during the dissolution of the neodymium
bromide. Buchner funnel with hard paper filter was used to
separate the leach solution from the sediments. Filtrates (leach
solutions) were collected in a 200 cm3 volumetric flask, and
filled by the solution of 0.05 M HCl to the mark. Then a
20 cm3 of the resulting solution was diluted 10 times in a
200 cm3 volumetric flask. Next, 10 cm3 of the diluted solution
was transferred to a conical flask and 10 cm3 of buffer solution
(CH3COOH/CH3COONa), pH = 5.6 was added. The pre-
pared solution was heated almost to boil (80 °C), and then four

Please cite this article in press as: Bounouri, Y. et al., Optimization and modeling of synthesis parameters of neodymium(III) bromide by dry method using full fac-
torial design analysis. Arabian Journal of Chemistry (2017), http://dx.doi.org/10.1016/j.arabjc.2017.05.003
Optimization and modeling of synthesis parameters of neodymium(III) bromide
Figure 1 Thermodynamic functions: (a) Standard enthalpy of reaction, (b) Standard entropy of reaction, and (c) Standard Gibbs free
energy of reaction.
drops of xylenol orange solution were added. The chemical
analysis of the content of Nd was performed by a complexo-
metric titration with a standard EDTA solution until the color
changed from purple–red to light yellow. The titration was
repeated 3 times.
3. Full factorial designs
A full factorial design is an experimental design with a number
of levels limited to two (low and high) for each factor; it takes
into account all the combinations between the levels of factors
during the experiment. The full factorial design allows model-
ing of the first degree with or without interactions and it
quickly finds the application limits when the number of factors
increases. This design also allows us to determine the effects of
the factors on the response and the effects of interactions
between different factors (Montgomery, 2012).
4. Results and discussion
4.1. Thermodynamic aspect of the reaction
Before synthesis of NdBr3 by sintering brominating with NH4-
Br, we performed a thermodynamic study of the reaction to
Please cite this article in press as: Bounouri, Y. et al., Optimization and modeling of synthesis parameters of neodymium(III) bromide by dry method using full fac-
torial design analysis. Arabian Journal of Chemistry (2017), http://dx.doi.org/10.1016/j.arabjc.2017.05.003
3
determine the standard thermodynamic parameters such as
enthalpy, entropy and the standard Gibbs free energy of this
reaction. These thermodynamic parameters provided informa-
tion about the exothermic or endothermic synthesis process,
the degree of disorder, and clarified the possibility of sponta-
neous synthesis process.
The synthesis of NdBr3, from Nd2O3 and NH4Br by dry
route, can be described by the following reaction:
Nd2 O3 ðsÞ þ 6 NH4 Brðs; gÞ ! 2 NdBr3 ðsÞ þ 6 NH3 ðgÞ
þ 3 H2 Oð‘; gÞ ð1Þ
The standard thermodynamic quantities (Dr H0T ,Dr S0T ;Dr G0T )
were calculated using the thermodynamic data obtained from
the literature (Lide, 2007; Barin, 1995). The results of above
calculation are presented in Fig. 1.
The results of Fig. 1a show that the reaction is endothermic
between room temperature and T = 606 K (sublimation tem-
perature of NH4Br). The sudden increase of enthalpy observed
at 373 K is associated with the passage of water from liquid to
a gaseous state.
Fig. 1b shows that the entropic contribution is positive over
the entire temperature range, this is due to the increase in dis-
order, which can be explained by the increase in the number of
moles of gas.
4 Y. Bounouri et al.

120 0.2
Td = 333.065 °C
0
100 DTG
-0.2

80 -0.4

dm/dT (%/°C)
-0.6
m (%) 60
-0.8

40 -1

-1.2
20
TG % -1.4

0 -1.6
40 197 364 530
T (°C)

Figure 2 Curves TG-DTG of ammonium bromide NH4Br obtained at 10 °C/min under nitrogen atmosphere.

Figure 3 Curves TG-DTG obtained at 10 °C/min under nitrogen atmosphere of neodymium oxide Nd2O3.

The free enthalpy of reaction as a function of the tempera-
ture was calculated according to the equation:
Dr G0T ¼ Dr H0T  TDr S0T
Fig. 1c shows that the Dr G0T decreases with increase in temper-
ature. This means that the synthesis of NdBr3 is promoted by
an increase in temperature. Also, we can deduce graphically an
inversion temperature T = 571 K, beyond which the reaction
is favorable.
4.2. Thermal analysis of reagents by TG–DTG
The two reagents (Nd2O3 and NH4Br) used for the synthesis of
NdBr3, have been analyzed with TG–DTG in order to verify
their stability in function of the temperature. The TG–DTG
curves obtained with heating rate 10 °C/min under a nitrogen
atmosphere are shown in Figs. 2 and 3.
ð2Þ
Fig. 2 shows that NH4Br begins to lose the weight at 179 °C
and greater weight loss, corresponding to decomposition tem-
perature according to the reaction (3), was observed at 333 °C.
NH4 BrðsÞ ! NH3 ðgÞ þ HBrðgÞ ð3Þ
Sintering brominating of neodymium oxide takes place with
NH4Br and also with HBr formed during thermal decomposi-
tion of NH4Br. (Mendil et al., 2013; Chen et al., 2008).
The curves TG–DTG of Nd2O3 (Fig. 3) shows that the
oxide does not lose any weight and that during this process
the oxide remained stable. This observation confirms the

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Optimization and modeling of synthesis parameters of neodymium(III) bromide 5

40

35

30

25
R (%)

20

15

10

0
0 20 40 60 80 100 120 140
t (min)
Figure 6 Effect of the temperature on variations of yield.
Figure 4 Effect of contact time on variations of yield.

50 Table 1 Factors and levels used in the factorial design.

45 Factors Low level Center High level
40 (1) level (0) (+1)
35 (x1 ) Contact time (min) 10 35 60
(x2 ) Stoichiometry in moles 1:6 1:15 1:24
30
R (%)

(Nd2O3:NH4Br)
25 (x3 ) Temperature (°C) 250 325 400
20
15
10
5 moles is the number of moles corresponding to a yield of
0
100% calculated from the mass of the neodymium oxide.
0 [1 : 6] [1 : 18] [1 : 30] The results are presented in Fig. 4.
This figure shows that the yield of the reaction R (%)
Stoichiometry
increases with the increase in reaction time up to 60 min.
Figure 5 Effect of the stoichiometry on variations of yield. Beyond this value, the yield remains almost constant and sta-
bilizes at an average of 30%. Therefore, the optimum contact
time of this reaction is 60 min, and for this reason, we set the
contact time to 60 min in order to study the effect of the stoi-
literature information concerning the lanthanide oxides chiometry and temperature.
(Sarbak et al., 2005).
4.3.2. Influence of the stoichiometry
4.3. Optimization of the synthesis parameters The study of this parameter was carried out in order to see the
effect of excess NH4Br on the reaction yield. It is based on the
In this work, we studied the influence of three main synthesis variation of the stoichiometry in moles of Nd2O3:NH4Br from
parameters (contact time, stoichiometry and temperature) on 1:6 to 1:30. The two other parameters were kept constant
the reaction yield. (t = 60 min and T = 250 °C). The results obtained are repre-
sented in Fig. 5.
4.3.1. Influence of the contact time Increase in the reaction yield R (%) was observed with
The study of contact time influence on the reaction yield was excess of NH4Br up to the molar ratio Nd2O3:NH4Br = 1:24.
realized by varying it from 10 to 120 min while maintaining Beyond this value, the yield was stabilized at a level of about
the two other parameters constant (the molar ratio Nd2O3: 46%. The optimal molar ratio Nd2O3:NH4Br was found to
NH4Br = 1:6 and experimental temperature T = 250 °C). be 1:24.
The reaction yield, noted R, was calculated with the follow-
ing equation: 4.3.3. Influence of the temperature
The thermodynamic study of the synthesis reaction of NdBr3
number of experimental moles
R¼  100 ð4Þ showed that the synthesis is promoted by an increase in tem-
number of theoretical moles
perature. According to this result, we have chosen to vary
The number of experimental moles is the number of moles of the temperature from 250 to 450 °C, and kept the two other
NdBr3 obtained during reaction. The theoretical number of parameters at their optimum level (t = 60 min and molar ratio

Please cite this article in press as: Bounouri, Y. et al., Optimization and modeling of synthesis parameters of neodymium(III) bromide by dry method using full fac-
torial design analysis. Arabian Journal of Chemistry (2017), http://dx.doi.org/10.1016/j.arabjc.2017.05.003
6 Y. Bounouri et al.

The mathematical model in the coded form for the full fac-
Table 2 Design matrix and the results of the 23 full factorial
torial design 23 is given as follows:
design.
Experiments x1 x2 x3 R (%) R^ ¼ b0 þ b1 x1 þ b2 x2 þ b3 x3 þ b12 x1 x2 þ b13 x1 x3
1 1 1 1 7.40 þ b23 x2 x3 þ b123 x1 x2 x3 ð5Þ
2 1 1 1 30.84
3 1 1 1 14.99 where R^ is the predicted reaction yield, b0 is the global mean, bi
4 1 1 1 46.04 represents the other regression coefficients andx1 ,x2 ,x3 , stands
5 1 1 1 21.84 for contact time, stoichiometry and temperature, respectively.
6 1 1 1 79.76 The results obtained from the 14 experiments are shown in
7 1 1 1 30.07 Table 2, with the low (1), center (0), and high (+1) levels as
8 1 1 1 97.80 specified in Table 1.
9 0 0 0 47.40
10 0 0 0 48.55
4.4.1. Statistical analysis
11 0 0 0 48.17
12 0 0 0 49.32 After realization of the 14 experiments, we have calculated the
13 0 0 0 47.01 various coefficients of the model (bi ), and then we have deter-
14 0 0 0 50.86 mined the main effects and interactions between different fac-
tors. This effect which represents the difference between the
average value of the response (R) at the high level (+) and
the average value of the response at low level () was deter-
Nd2O3:NH4Br = 1:24). Fig. 6 represents the experimental mined using the formula (6) (Cavalitto and Mignone, 2007).
results of this study. P P
It is evident that an increase in temperature up to 400 °C Ei ¼
RðiþÞ

RðiÞ
ð6Þ
has a positive effect on the reaction yield. Beyond this value, n n
the yield decreases slightly. This is probably due to the loss
of NH4Br related to its decomposition at high temperatures
(Mendil et al., 2013). As a result, the optimum temperature
for synthesis of NdBr3 by sintering brominating with NH4Br
is 400 °C for which yield reaches 97.80%.

4.4. Factorial design analysis

After optimization of the three factors influencing the reaction

yield of the synthesis of NdBr3, we have applied the experiment
design method to model the reaction yield depending on the
three factors. This method allows us to find a mathematical
model that links the reaction yield to the three factors, and
allows us to examine the main and interaction effects of factors
on the reaction yield.
In this study, a full factorial design 23 with six experiments
at the central point and therefore a total of 14 experiments
were used. The replication of experiments in central point is
in order to evaluate the experimental error (Mendonça et al.,
2011). The high, center and low levels defined for the 23 facto-
rial designs were listed in Table 1. The low and high levels of
the factors were selected according to the optimization results. Figure 7 Pareto chart of the standardized effects.

Table 3 Statistical parameters for 23 designs.

Term Effects Coefficients Standard error ti Significance
b0 41.09 41.09 0.9506 83.15 S
b1 45.03 22.51 0.9506 45.55 S
b2 12.27 06.13 0.9506 12.41 S
b3 32.55 16.28 0.9506 32.95 S
b12 04.36 02.18 0.9506 4.41 S
b13 17.79 08.90 0.9506 18.01 S
b23 00.87 00.44 0.9506 0.89 NS
b123 00.55 00.28 0.9506 0.57 NS
S: Significant, NS: Not Significant.

Please cite this article in press as: Bounouri, Y. et al., Optimization and modeling of synthesis parameters of neodymium(III) bromide by dry method using full fac-
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Optimization and modeling of synthesis parameters of neodymium(III) bromide 7

Table 4 Analysis of variance-reduced model fit for reaction yield.

Experiments Ri R^i ðRi  R^i Þ
2
ðR^i  RÞ
2 
ðRi  RÞ
2

1 7.40 7.25 0.022 1145.32 1135.19

2 30.84 30.11 0.533 120.62 105.12
3 14.99 15.15 0.026 673.02 681.35
4 46.04 46.73 0.476 31.78 24.48
5 21.84 22.01 0.029 364.15 370.66
6 79.76 80.47 0.504 1550.58 1495.17
7 30.07 29.91 0.026 125.05 121.50
8 97.80 97.09 0.506 3135.71 3215.84
SUM – – SSE = 2.121 SSR = 7146.222 SST = 7149.300

Figure 8 Plot of the measured and model predicted values of the response variable.

regression equation because their influence on the reaction

yield is negligible (Erto et al., 2010).
The ti value which represents the ratio of the coefficient to
the estimated parameter and standard deviation residual are
calculated using the following equation:
jbi j
ti ¼ sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P  ð7Þ
m 2
ðR0j R0 Þ
1 j¼1
N m1

where bi : coefficient, N: number of experiments (N = 8), m:

Figure 9 Residual plots for reaction yield R (%).
where Ei is the effect of the variable, R is the experimental
response, and n is the number of experiments at each level
( or +).
The significance of the different calculated coefficients has
been checked by the Student’s t-test, which allows us to deter-
mine whether among the coefficients of the model, there are no
significant coefficients, which will be eliminated from the
number of experiments at the central point (m = 6), R0j :
observed value of reaction yield at the j central point, R0 : mean
reaction yield at the central point.
The regression coefficients, the effects and t values are
shown in Table 3.
For a 95% confidence level and 5 degrees of freedom (m-1),
the tabulated value of STUDENT (tcrit value) is 2.57.
The results are illustrated by means of Pareto charts
(Fig. 7). The vertical line in Pareto charts indicates minimum
statistically significant effect magnitude for a 95% confidence
level. The effects which have ti less than 2.57 are statistically
insignificant (Montgomery, 2012; Carmona et al., 2005).
According to the Pareto chart (Fig. 7), the interaction, sto-
ichiometry - temperature (coded x2 x3 ) and time-stoichiometry-
temperature (coded x1 x2 x3 ) are insignificant for a 95% confi-
dence level.

Please cite this article in press as: Bounouri, Y. et al., Optimization and modeling of synthesis parameters of neodymium(III) bromide by dry method using full fac-
torial design analysis. Arabian Journal of Chemistry (2017), http://dx.doi.org/10.1016/j.arabjc.2017.05.003
8 Y. Bounouri et al.

Thus, the reduced model, represented by (Eq. (5)) in terms X

N
ðRi  R^i Þ
2
of coded parameters after excluding the insignificant terms for SSE ¼ ð11Þ
i¼1
the predicted reaction yield R^ (%) is as follows:
These parameters are shown in Table 4.
R^ ¼ 41:09 þ 22:51x1 þ 6:13x2 þ 16:28x3 þ 2:18x1 x2 The validity of the regression equation is based on the sta-
þ 8:90x1 x3 ð8Þ tistical of Fisher, which consists in comparing of F-value
defined as the ratio between the mean-square-effect and the
mean-square-error, and the tabulated value of the F-
4.4.2. Variance analysis (ANOVA) distribution at a level of significance and a certain number
The significance and adequacy of the regression model after degrees of freedom.
excluding insignificant coefficients was evaluated by the analy- The value of F is calculated by the following equation:
sis of variance (ANOVA) (Sen and Swaminathan, 2004). PN
ðR^i  RÞ =ð‘  1Þ
2
The ANOVA is based on the comparison of the variation SSR=ð‘  1Þ
F¼ ¼ P i¼1 ð12Þ
SSE=ðN  ‘Þ N ^ 2
i¼1 ðRi  Ri Þ =ðN  ‘Þ
associated with the model that represents the sum of the quad-
ratic variation of the experimental yield (R) and the predicted
^ to the experimental average yield (R) and variation where ‘: number of the significance parameters.
yield (R)
The model is a good predictor of the experimental results if
associated with experimental error which represents the sum
the F-value is greater than the tabulated value of the F-
of the squared residual between the experimental and predicted
distribution (Yetilmezsoy et al., 2009; Liu et al., 2004).
yields (Kasiri and Khataee, 2011).
The calculated F-value for reaction yield ‘‘F = 1347.57” is
The sum of squared total (SST), sum of squares for regres-
much greater than the tabulated (F ¼ 19:3 at the 95% signifi-
sion (SSR) and sum of squared errors (SSE) were computed
cance), the regression equation is thus very significant on the
from the reaction yield as follows (Tinsson, 2010):
response, and the adjustment of the model is adequate.
X
N
2
SST ¼ ðRi  RÞ ð9Þ 4.4.3. Correlation coefficients
i¼1
The correlation coefficient or determination coefficient (R2) is
X
N the ratio between the variation due to the regression and the
ðR^i  RÞ
2
SSR ¼ ð10Þ total variation, this coefficient enable us to check the
i¼1

Figure 10 Main effects plot for reaction yield R (%): (a) contact time, (b) stoichiometry, and (c) temperature.

Please cite this article in press as: Bounouri, Y. et al., Optimization and modeling of synthesis parameters of neodymium(III) bromide by dry method using full fac-
torial design analysis. Arabian Journal of Chemistry (2017), http://dx.doi.org/10.1016/j.arabjc.2017.05.003
Optimization and modeling of synthesis parameters of neodymium(III) bromide 9

correlation between the experimental and the predicted when the sample size is not very large and the number of terms
responses (Liu and Chiou, 2005; Santos and Boaventura, in the model is not great, the adjusted R2Adj may be smaller than
2008; Deming and Morgan, 1993), it is calculated as follows: R2 (Santos and Boaventura, 2008).
PN In our study, the value of R2Adj (0.993) was found very close
ðR^i  RÞ
2
SSR
R ¼
2
¼ Pi¼1 2
ð13Þ to the corresponding value R2.
SST N
i¼1 ðRi  RÞ

The calculated R2 (R2 = 0.999) is very close to 1, which
explains a strong linear relationship between the experimental
responses and that given by the model. The values of R2 indi-
cate that the model does not explain only about 0.001 of the
variations. This result is confirmed by the representation of
the experimental results and those calculated by the model
(Eq. (8)) in Fig. 8, which shows a good correspondence
between the experimental and predicted values.
The goodness of fit of the model was also checked by
adjusted coefficient R2Adj (Eq. (14)), which corrects the correla-
tion coefficient value R2 for the sample size and the number
of terms in the model.
N1
R2Adj ¼ 1  ð1  R2 Þ
N‘1
4.4.4. Residual analysis
The residuals analysis, which represents the difference between
the experimental and predicted responses, allows us to repre-
sent the unexplained part of the model and check whether
there is a failure in the latter. This test consists of analyzing
the plot of observed residues depending on the predicted
responses (Fig. 9) (Kasiri and Khataee, 2011; Sado and
Sado, 2000).
The look of the graph shows a random distribution of
points, confirming the nonexistence of a relationship between
predicted responses and residue. So the model of first level
that we have established well explains the experimental
results (Kasiri and Khataee, 2011; Goupy and Creighton,
ð14Þ 2006).

(a) (b)

70
(c) 400 °C
60

50

40
R (%)

30 250 °C

20

10

0
0 [1:6] [1:24]
Stoichiometry

Figure 11 Interaction effects plot: (a) time/stoichiometry, (b) time/temperature, and (c) stoichiometry/temperature.

Please cite this article in press as: Bounouri, Y. et al., Optimization and modeling of synthesis parameters of neodymium(III) bromide by dry method using full fac-
torial design analysis. Arabian Journal of Chemistry (2017), http://dx.doi.org/10.1016/j.arabjc.2017.05.003
10
4.5. Main and interaction effects
A main effect can be defined as the effect of one factor on the
response, ignoring the effects of all other factors, it represents
the change in the response when the factor changes from low
to high levels. The effect of a factor is positive if the response
R (%) increases when the factor changes from low to high
levels. Otherwise (the response R (%) decreases when the fac-
tor changes from low to high levels) the effect is negative
(Ponnusami et al., 2007).
The main effects of the experimental results for the respec-
tive low and high levels of contact time, molar ratio and tem-
perature were illustrated in Fig. 10.
From the graph (Fig. 10), we can see that an increase in
contact time (a), stoichiometry (b), temperature (c), from low
to high levels resulted in an increase in the reaction yield R
(%). This indicates that all factors have a positive effect on
the response (Palanikumar et al., 2009; Lorenzen and
Anderson, 1993).
Contrast to the main effect, the interaction effect represents
the effect of a factor on the response as a function of other fac-
tors. An interaction between two factors is significant when the
effect of a factor on the response depends on the level of the
other factor, i.e. whether the lines of the two factors are not
parallel (Lazić, 2004; Mathialagan and Viraraghavan, 2005).
The interactions between factors were illustrated in Fig. 11.
Fig. 11 shows the significant interactions between contact
time and stoichiometry (Fig. 11a), as well as between the con-
tact time and the temperature (Fig. 11b). However, the interac-
tion between stoichiometry and temperature (Fig. 11c) is
neglected (the lines are almost parallel). These plots also indi-
cate that the interaction between the contact time and the tem-
perature (x1 x3 ) is stronger than between the contact time and
stoichiometry (x1 x2 ). These plots also show that the effect of
the contact time is larger when the temperature and the stoi-
chiometry are at high (+1) levels.
5. Conclusion
In these study, the synthesis parameters (contact time, stoichiometry
and temperature) of neodymium(III) bromide by dry method are opti-
mized. According to the results, the optimum conditions for the syn-
thesis of NdBr3 are as follows: contact time (t = 60 min),
stoichiometry in moles (Nd2O3:NH4Br = 1:24) and temperature
(T = 400 °C), for which the reaction yield reached 97.80%.
The full factorial design was used to allow the evaluation of the
most important factors for synthesis of neodymium(III) bromide. This
modeling leads to a first degree mathematical model, which relates the
yield to the three operating parameters. It has also shown that an
increase from lower to higher levels in factors has a significantly pos-
itive influence on reaction yield R (%), with presents of significant
interaction between contact time (t) and stoichiometry, and between
contact time (t) and temperature. The validity of this study was limited
to, contact time between 10 and 60 min, stoichiometry between 1:6 and
1:24 and temperatures between 250 and 400 °C.
Acknowledgments
The work was finances by a statutory activity subsidy from the
Polish Ministry of Science and Higher Education for the
Faculty of Chemistry of Wroclaw University of Technology.
Please cite this article in press as: Bounouri, Y. et al., Optimization and modeling of synthesis parameters of neodymium(III) bromide by dry method using full fac-
torial design analysis. Arabian Journal of Chemistry (2017), http://dx.doi.org/10.1016/j.arabjc.2017.05.003
Y. Bounouri et al.
Financial support by the Thematic Agency for Research in
Science and Technology (ATRST) from the Algerian Ministry
of Higher Education and Scientific Research is gratefully
acknowledged.
M. B and Y. B wish to thank the Department of Chemistry of
Wroclaw University of Technology for hospitality and support
during this work.
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