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MODELING AND OPTIMIZATION OF THE INHIBITION EFFICIENCY OF

Euphorbia heterophylla EXTRACTS BASED CORROSION INHIBITOR ОF MILD
STEEL CORROSION IN HCl MEDIA USING А RESPONSE SURFACE ME...

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 Journal of Chemical Technology and Metallurgy,
Odejobi Oludare 54, 1,Olatunde
J., Akinbulumo 2019, 217-232
A.

MODELING AND OPTIMIZATION OF THE INHIBITION EFFICIENCY

OF Euphorbia heterophylla EXTRACTS BASED CORROSION INHIBITOR ОF MILD
STEEL CORROSION IN HCl MEDIA USING А RESPONSE SURFACE METHODOLOGY

Odejobi Oludare J., Akinbulumo Olatunde A.

Chemical Engineering Department Received 14 October 2017

Obafemi Awolowo University, Ile- Ife Nigeria Accepted 09 February 2018
E-mail: tundeakinbulumo@gmail.com
dareodejobi@oauife.edu.ng

ABSTRACT

Response Surface Methodology (RSM) was used to study and statistically analyze the inhibition of mild steel corrosion
in hydrochloric acid media by an extract of Euphorbia heterophylla. The study was carried out in a hydrochloric acid
concentration range from 0.5M to 1.5M, at an extract concentration varying from 1 g L-1 to 2 g L-1, in the temperature
interval from 40oC to 70oC and immersion time ranging from 4 h to 7 h. The experimental data was analysed for consist-
ency and significance. Quadratic model equations were generated for both the inhibition efficiency and the corrosion rate.
The optimum conditions for the process were determined. The predicted inhibition efficiency was in agreement with the
experimental data. The optimization results showed that the inhibition efficiency of 89.8 % was obtained at the optimum
combination of the extract concentration, the acid concentration, the temperature and the immersion time. The corresponding
values were 1.97 g L-1, 0.5 mol L-1, 47.4oC, and 4.5 h. It was concluded that Euphorbia heterophylla is an effective corro-
sion inhibitor of mild steel corrosion in hydrochloric acid media, while RSM is suitable for its modeling and optimisation.
Keywords: inhibition optimization, Euphorbia heterophylla, inhibition efficiency, response surface methodology,
inhibition modeling, corrosion rate modeling.

INTRODUCTION alatifolium as an inhibitor for aluminium corrosion in

Corrosion is the degradation of metals when they
are in contact with the environment [1], and prevention
is the best way to combat it. This necessitates increas­ing
research into ways of preventing the damaging effects of
corrosion on metals and alloys [2]. There are numerous
methods for controlling the corrosion of metals but the
use of corrosion inhibitors is the best and the most con-
venient practical method among them [3-6]. Corrosion
inhibitors are organic and inorganic substances that are
added to the corrosive environment to reduce or elimi-
nate corrosion. Organic corrosion inhibitors are found
cheaper, biodegradable, renewable, more efficient and
environmentally friendly [1]. Extracts of plant materials
are widely reported to control the corrosion of various
metals such as mild steel [7, 8], but the optimization of
the process is scarcely reported [9, 10].
The use of Response Surface Methodology (RSM)
in optimizing the inhibition efficiency of Gorgronem
HCl solutions is reported by Njoku and Onyelucheya
[10]. They find that the linear and the quadratic effect
of the process variables are highly significant, as well as
the temperature and time interaction effects. The optimal
values of the acid concentration, the temperature, the
immersion time and the extract concentration provid-
ing inhibition efficiency of 74.14 % refer to 1.73 mol
dm-3, 328.6 K, 10.14 h and 1000 mg L-1, respectively.
Onukwuli and Omotioma [11] report the optimization of
the inhibition efficiency of a mango extract as a corro-
sion inhibitor of mild steel in 1.0 M H2SO4 using RSM.
The authors conclude that the mango extract exhibits
an optimum inhibition efficiency of 74.09 % at 0.97 g
L-1, 305.35 K and 22.76 h referring to the extract con-
centration, the temperature and the time, respectively.
The authors determine that there is a close agreement
between the predicted and the experimental data, and
conclude that RSM is suitable for modeling and predic-
tion of the corrosion rate.

217
 Journal of Chemical Technology and Metallurgy, 54, 1, 2019
Salam et al. [12] study the optimization of the
operating conditions affecting the microbiologically
influenced corrosion of mild steel exposed to crude oil
environments using the response surface methodology.
The results obtained show that pH has the most influen-
tial effect on the response and that the predicted values
have a reasonable agreement with the experimental data
with R = 0.9660 and Adj-R = 0.9516. The study reveals
that RSM design is an efficient statistical technique for
predicting the optimum operating conditions in crude
oil environments required to minimize mild steel cor-
rosion in oil pipelines by incorporating all factors under
consideration.
Elkhotfi et al. [ 13 ] report their work on the opti-
mization of the inhibitor efficiency of triazole on corro-
sion of mild steel in 1M HCl. They conclude that of the
three factors considered, the temperature has the least
impact, while the inhibitor concentration has the high-
est one on the inhibitor efficiency. A statistical analysis
of the corrosion inhibition of water hyacinth on mild
steel in an acidic medium is reported by Omoruwou et
al. [14]. The response surface methodology is used to
assess the effects of the process experimental variables
influencing the corrosion rate, and to find the optimum
combinations of the factors considered. The optimum
process variables obtained from the quadratic model
developed refer to an inhibitor concentration of 1.50 g
L-1, an exposure time of 8 h, and a temperature value
of 60°C with a predicted inhibitor’s efficiency value of
82.89 %. According to the researchers the mild steel
corrosion inhibition is achieved through the double bond
adsorption of the carbonyl group present in the inhibitor
phytochemical constituent.
Afzalkhah et al. [15] design the optimization of
the influencing parameters on the corrosion inhibition
Table 1. Summary of the design parameters employed.
Factor Minimum
Units Actual
Extract concen.,(X1) g L-1 1.00
Acid Concen., (X2) Mol dm-3 0.50
0
Temperature(X3) C 40.00
Time (X4) Hr 3.00
218
efficiency of 2-(2-hydroxyphenyl)-benzothiazole using
electrochemical impedance spectroscopy (EIS) and
quantum chemical calculations. The optimum values
obtained by the response surface methodology (RSM)
refer to an inhibitor concentration of 433.7 μM, a hydro-
chloric acid concentration of 3.38 mol/l, and an ethanol
concentration of 0.36 mol/l.
The study, the analysis, the modeling and the optimi-
zation of the corrosion inhibitive behavior of Euphorbia
heterophylla extract is reported in this work. A four- fac-
tor design is employed in the simultaneous modeling
of the inhibition efficiency and the corrosion rate as an
improvement over the previous reported works. The
conditions studied refer to mild steel in hydrochloric
acid solutions of a concentration varying from 0.5 M to
1.5 M. The extract concentration ranged from 1.0 gL-1
to 2.0 g L-1, the temperature interval was from 40oC to
70oC, while the immersion time varied from 4 h to 7 h.
The significance of these factors and their interaction is
investigated and discussed. Euphorbia heterophylla is
acknowledged for its medicinal values but its use as a
corrosion inhibitor has not been so far reported. RSM
is employed in the experiment design, the analysis, the
modeling and the process parameters optimization.
EXPERIMENTAL
Materials
The materials used in this research work were as fol-
lows: dried and powdered Euphorbia heterophylla plant,
a stock solution of hydrochloric acid, ethanol, a plastic
bowl, a sieve, a rotatory evaporator, a freeze dryer, a
refrigerator, mild steel samples, emery papers, 1 dm3
volumetric flask, 250 cm3 beaker, a thermometer, a water
bath, a hot plate, thread, a micrometer screw gauge, a
digital mass balance and Design Expert, version 8.0.3.
Mean Maximum
coded Actual coded Actual coded
-1 1.50 0 2.00 1
-1 1.00 0 1.50 1
-1 55.00 0 70.00 1
-1 5.00 0 7.00 1
 Odejobi Oludare J., Akinbulumo Olatunde A.
Extraction Process
The plant, Euphorbia heterophylla, was washed,
chopped into small pieces, air dried and ground to
powder. 300 g of the latter were transferred to 2000 ml
(95 %) ethanol for a solvent extraction. The mixture
was filtered and the resulting solution (filtrate) was
concentrated under vacuum using Rotatory Evaporator
(Buchi, R11). The product was freeze dried to remove
the water and stored in the freezer.
Preparation of the Inhibitor Solution
The required acid concentrations were obtained
from the stock solution according to dilution principle.
The specified mass of the extract was dissolved in the
stipulated hydrochloric acid solution according to the
parameters run.
Preparation of the Mild Steel Samples
A mild steel rod was machined into a cylindrical shape
with a lathe machine and was cut into 2 cm x 1 cm pieces.
The metal samples were machined to obtain a regular
shape and a smooth surface. Then they were mechanically
polished using an emery paper of different grades (P30D,
P320C, P600A, and P800A) to remove completely the
existing corrosion and to obtain a glass-like surface.
Experiment Design
RSM was used to design the experiment. The sum-
mary of the design matrix is given in Table 1. Using the
Central Composite Design (CCD) modeling technique
of Design Expert 8.0.3., thirty experimental runs were
generated for the four-factor design.
Weight Loss Experiment
The weight loss experiment included:
l machining the mild steel into cylindrical coupons;
lpolishing the cylindrical mild steel samples with
emery papers;
l washing the samples with water and ethanol to
remove dirt, corrosion products and grease;
l measuring of the initial mass and the dimensions
using a digital balance F023455 and a micrometer screw
gauge;
l suspending the mild steel samples in the electro-
lyte;
l measuring of final mass and the weight loss;
l calculating the inhibition efficiency and the cor-
rosion rate.
The beakers were placed in a thermostat-regulated
water bath. At a regulated temperature, the mild steel
samples were withdrawn after a stipulated immersion
time, brushed in running water, washed with acetone,
dried and reweighed. There was a control experiment
for each run in which no extract was added to the acid
solution (uninhibited). From the initial and final masses
of the mild steel samples, the weight (mass) loss was
calculated. The experiments were carried out in dupli-
cates and the mean weight loss was obtained. It provided
the calculation of the inhibition efficiency (I.E ) , % and
the corrosion rate (C R ) , mmyr-1 on the ground of Eqs. (1)
and (2) [10, 16, 17].
w0 − w
I
.E = × 100 (1)
w0
87.6w
CR = (2)
A×t×D
where w0 was the weight loss of the inhibited mild steel
in mg, A was the area of the mild steel (cm2), t was the
immersion time (h) and D was the mild steel density (i.e
7.86g cm-3). This weight loss method has been widely
used in inhibition efficiency estimation [8,10,16-18].
Statistical Analysis and Modeling of the Inhibition
Efficiency
The experimental data (the inhibition efficiency and
the corrosion rate) obtained was analyzed using Design
Expert 8.0.3 software to obtain the variance analysis,
ANOVA, the regression analysis and the response surface
plots of the interaction of the factors. The linear, quadratic
and polynomial interactive effects of the process vari-
ables on the responses were analyzed and their respective
significance evaluated by ANOVA test. The p-value (≤
0.05) was used as the measure of the significance of the
regression coefficient. The regression model and the
adequacy of the model were tested by comparing the
actual R-Squared and the predicted R-squared values.
The model with the highest and close R-squared values
was selected. The predicted responses (the inhibition effi-
ciency and the corrosion rate) were evaluated and plotted
against the actual one to check the correlation between
the experimental (actual) and predicted responses.
219
 Journal of Chemical Technology and Metallurgy, 54, 1, 2019

Table 2. Design optimisation targets.

Factor Goal Lower Limit Upper Limit
X1:Extract Conc (g/l) in range 1.0 2
X2:Acid Conc.(mol/dm3) in range 0.5 1.5
X3:Tempt (0C) in range 40 70
X4:Time (Hr) in range 3 7
Y1:Inhibition Efficiency (%) maximize
Y2:Corrosion Rate (mm/yr) minimize

Table 3. Weight loss experiment results.

Run X1 Extract X2 Acid X3 Tempt X4 Time Response 1 Response 2
Conc. (g/l) Conc. (M) (0C) (Hr) Inhibition Corrosion Rate
Efficiency (%) (mm yr-1)
1 1.00 1.50 70.00 7.00 45.97 139.88
2 1.00 1.50 40.00 3.00 41.50 14.86
3 2.00 0.50 40.00 3.00 83.30 4.087
4 2.00 0.50 70.00 7.00 53.77 155.45
5 1.00 0.50 70.00 3.00 65.72 41.38
6 1.00 0.50 40.00 7.00 85.71 5.355
7 1.50 1.00 55.00 5.00 70.57 26.473
8 2.00 1.50 40.00 7.00 52.00 4.242
9 1.50 1.00 55.00 5.00 79.40 17.77
10 2.00` 1.50 70.00 3.00 35.88 369.75
11 2.00 0.50 70.00 3.00 71.88 112.79
12 1.50 1.00 55.00 5.00 79.40 17.689
13 1.50 1.00 55.00 5.00 76.47 20.383
14 2.00 1.50 40.00 3.00 32.00 71.10
15 2.00 1.50 70.00 7.00 12.57 283.086
16 1.00 1.50 70.00 3.00 36.80 199.72
17 2.00 0.50 40.00 7.00 66.67 9.296
18 1.00 0.50 40.00 3.00 25.00 12.35
19 1.00 0.50 70.00 7.00 57.30 74.22
20 1.00 1.50 40.00 7.00 53.34 12.93
21 1.50 2.00 55.00 5.00 47.00 180.57
22 1.50 1.00 55.00 1.00 69.23 26.56
23 1.50 0.00 55.00 5.00 100.00* 0.0*
24 1.50 1.00 55.00 5.00 78.57 15.206
25 1.50 1.00 55.00 5.00 78.57 15.977
26 2.50 1.00 55.00 5.00 75.00 145.11
27 1.50 1.00 85.00 5.00 45.00 310.07
28 1.50 1.00 55.00 9.00 73.40 20.586
29 1.50 1.00 25.00 5.00 66.67 2.706
30 0.50 1.00 55.00 5.00 77.27 8.984
* obtained when the acid concentration, X2 = 0.0 mol/dm3 ( i.e non acidic medium).

220
 Odejobi Oludare J., Akinbulumo Olatunde A.
Optimization Technique
The objective of the optimisation was to find the best
process parameters that would give maximum inhibition
efficiency and minimum corrosion rate. After developing
the regression models for both the inhibition efficiency
and the corrosion rate, RSM numerical optimisation
techniques using desirability function, d (where 0 ≤ d
≤ 1) were applied. The desirability function optimisa-
tion technique was an attractive method for industrial
processes optimisation [19]. The value of d increased
with the increase of the optimisation desirability.The
optimization targets presented in Table 2 were used as
the basis for the optimization of the process.
RESULTS AND DISCUSSION
The results from the weight loss experiment are pre-
sented in Table 3. It is evident that the highest inhibition
efficiency of 85.7% is obtained at 40oC in 0.5 M HCl at
an extract concentration of 1.0 g L-1 and an immersion
time of 7 h. This highest inhibition efficiency is reached
when the acid concentration and the temperature have
their lowest values. The observed results trend indi-
cates that the protective film provided by the inhibitor
is more effective when the acid concentration and the
temperature of the corrosive medium are at the lowest
level. On the other hand, the lowest inhibition efficiency
of 12.57 % is observed when the acid concentration and
the temperature reach their highest values, i.e. 1.5 mol
dm-3 and 70oC, respectively.
Statistical Analysis and Modeling of Inhibition Ef-
ficiency
The experimental results obtained for the inhibition
efficiency are statistically analyzed for consistency and
significance. ANOVA results referring to the inhibition
efficiency given in Table 4 show that eight out of the
twelve factor interactions are significant using P-Value
of ≤ 0.05 as a criterion. The acid concentration and the
temperature are significant factors implying that they
have a great influence on the inhibition efficiency of
the process. The Model F-value of 11.72 indicates that
the model is significant and that there is only a 0.01 %
chance that it could be attributed to noise. Therefore
this model can be used to predict the process inhibition
efficiency.
A second order polynomial model is selected due to
its significance and good R-squared value of 0.9036, Adj
R-Squared value of 0.8265, Pred. R-Squared of 0.6697
and Adequate Precision of 15.545. The values of the Ad-
justed R-Squared and the Predicted R-Squared are found
reasonably close because the difference is less than 0.2.
This shows that the experimental data obtained for the
inhibition efficiency are statistically consistent and the
second order polynomial model selected is suitable for
modeling. Adeq Precision measures the signal to noise
ratio. A value greater than 4 is desirable.The ratio of
15.545 indicates an adequate signal. The second order
polynomial model equation in terms of the coded values
of the process parameters is given as:
𝑌𝑌1(%) = 77.16 − 0.33𝑋𝑋1 − 12.72𝑋𝑋2 − 4.29𝑋𝑋3 +
+1.82𝑋𝑋4 − 5.44𝑋𝑋1 𝑋𝑋2 − 3.76𝑋𝑋1 𝑋𝑋3 − 6.96𝑋𝑋1 𝑋𝑋4 −
−7.29𝑋𝑋3 𝑋𝑋4 − 3.25𝑋𝑋1 2 − 3.91𝑋𝑋2 2 − 8.33𝑋𝑋3 2 − 4.46𝑋𝑋4 2
(3)
The coefficient terms in Table 4 of p-values greater
than 0.05 are considered insignificant and therefore are
removed from the regression model. Hence, the model
equation is reduced to:
𝑌𝑌1(%) = 77.16 − 12.72𝑋𝑋2 − 4.29𝑋𝑋3 −
−5.44𝑋𝑋1 𝑋𝑋2 − 6.96𝑋𝑋1 𝑋𝑋4 − 7.29𝑋𝑋3 𝑋𝑋4 −
−3.91𝑋𝑋 2 − 8.33𝑋𝑋 2 − 4.46𝑋𝑋 2 (4)
2 3 4
Predicted Versus Actual Inhibition Efficiency
The experimental data is also analyzed to check the
correlation between the experimental (actual) and pre-
dicted inhibition efficiency and the plot is shown in Fig.
1. The R2 value of 0.931 indicates that the data points on
the plot are distributed reasonably near the straight line.
This in turn provides to conclude that there is a good
relationship between the experimental and predicted
values of the response. The result also suggests that the
selected quadratic model is adequate in predicting the
response variables of the process [10].
221
 Journal of Chemical Technology and Metallurgy, 54, 1, 2019

Table 4. ANOVA referring to the inhibition efficiency.

Sum of Squares F Value P-value
Model 9141.74 11.72 <0.0001
X1-Extract 2.54 0.039 0.8459
X2-Acid Conc 3883.42 59.73 <0.0001
X3-Tempt 441.78 6.79 0.0198
X4-Time 79.17 1.22 0.2872
X1X2 473.61 7.28 0.0165
X1X3 225.83 3.47 0.0821
X1X4 774.93 11.92 0.0036
X3X4 849.58 13.07 0.0025
2
X1 290.48 4.47 0.0517
X22 419.98 6.46 0.0226
X32 1902.91 29.27 <0.0001
X42 545.42 8.39 0.0111
Lack of Fit 932.05 5.38 0.0959

Fig. 1. Plot of Predicted versus Actual Inhibition Efficiency.

Predicted Inhibition Efficiency at Different Acid
Concentrations
The inhibition efficiences are predicted at different
combinations of parameter levels using the model equa-
tion. Table 5 shows that the highest inhibition efficiency
of 88.5 % is obtained in 0.5 M of hydrochloric acid.
According to Table 6, the highest inhibition efficiency
of 78.6 % is obtained in 1.0 M hydrochloric acid. The
highest inhibition efficiency of 67.37 % in Table 7 is
obtained in 1.5 M hydrochloric acid. All these results

222
 Odejobi Oludare J., Akinbulumo Olatunde A.

Fig. 2. 3-D Surface Plot for Inhibition Efficiency, Acid Fig. 3. 3-D Surface Plot for Inhibition Efficiency, Im-
Concentration and Extract Concentration. mersion Time and Temperature.

Fig. 4. 3-D Surface Plot for Inhibition Efficiency, Tem- Fig. 5. 3-D Surface Plot for Inhibition Efficiency, Im-
perature and Extract Concentration. mersion Time and Extract Concentration.

Fig. 6. 3-D Surface Plot for Inhibition Efficiency, Fig. 7. 3-D Surface Plot for Inhibition Efficiency, Im-
temperature and Acid Concentration. mersion Time and Acid Concentration

223
 Journal of Chemical Technology and Metallurgy, 54, 1, 2019

Table 5. Predicted Inhibition efficiencies at 0.5 M HCl.

X1(Extract conc) X2 (Acid conc) X3(Tempt) X4(Time) Y1(%IE)

-1 -1 -1 -1 49.28
0 -1 -1 -1 68.36
1 -1 -1 -1 80.94

-1 -1 -1 0 45.91
0 -1 -1 0 59.55
1 -1 -1 0 66.69

-1 -1 -1 1 34.72
0 -1 -1 1 42.92
1 -1 -1 1 44.62

-1 -1 0 -1 64.37
0 -1 0 -1 79.69
1 -1 0 -1 88.51*

-1 -1 0 0 62.80
0 -1 0 0 74.36
1 -1 0 0 79.42

-1 -1 0 1 69.81
0 -1 0 1 81.93
1 -1 0 1 87.55

-1 -1 1 -1 81.42
0 -1 1 -1 86.58
1 -1 1 -1 85.24

-1 -1 1 0 77.61
0 -1 1 0 85.97
1 -1 1 0 87.83

-1 -1 1 1 81.93
0 -1 1 1 83.33
1 -1 1 1 78.23

show that the inhibition efficiency decreases with
the acid concentration increase. The highest inhibi-
tion efficiency is obtained at 55oC for all acid con-
centration considered. This suggests that Euphorbia
heterophylla extract is very effective as a corrosion
inhibitor of mild steel corrosion at moderate tempera-
tures when the acid concentration is maitained at the
lowest possible value.
3-D Surface Plots for the Inhibition Efficiency, the
Extract Concentration, the Acid Concentration, the
Temperature and the Immersion Time
Fig. 2 shows the 3-D surface plot for the inhibition
efficiency, the acid concentration and the extract con-
centration keeping the temperature and the immersion
time at their mean values of 55oC and 5.5 h, respectively.
The plot indicates that the inhibition efficiency increases

224
 Odejobi Oludare J., Akinbulumo Olatunde A.

Table 6. Predicted Inhibition Efficiencies at 1.0 M HCl.

X1 X2 X3 X4 Y1
(extract conc) (acid conc.) (tempt.) (time) (% IE)

-1 0 -1 -1 68.75
0 0 -1 -1 73.35
1 0 -1 -1 71.45

-1 0 -1 0 65.78
0 0 -1 0 63.42
1 0 -1 0 54.56

-1 0 -1 1 55.25
0 0 -1 1 56.49
1 0 -1 1 51.23

-1 0 0 -1 66.86
0 0 0 -1 61.14
1 0 0 -1 48.92

-1 0 0 0 74.24
0 0 0 0 77.16
1 0 0 0 73.58

-1 0 0 1 78.56
0 0 0 1 74.52
1 0 0 1 63.98

-1 0 1 -1 61.00
0 0 1 -1 70.88
1 0 1 -1 74.26

-1 0 1 0 63.05
0 0 1 0 60.53
1 0 1 0 51.51

-1 0 1 1 49.81
0 0 1 1 54.25
1 0 1 1 52.19

slightly with the extract concentration increase. How- Fig. 3 shows the 3-D surface plot for the inhibition
ever the maximum inhibition efficiency is predicted at efficiency, the immersion time and the temperature while
the lowest acid concentration and the highest extract the two other factors, the acid concentration and the ex-
concentration combination. tract concentration are kept at their mean values of 1.0

225
 Journal of Chemical Technology and Metallurgy, 54, 1, 2019

Table 6. Predicted Inhibition Efficiencies at 1.0 M HCl.

X1 X2 X3 X4 Y1
(extract conc) (acid conc.) (tempt.) (time) (% IE)

-1 0 -1 -1 68.75
0 0 -1 -1 73.35
1 0 -1 -1 71.45

-1 0 -1 0 65.78
0 0 -1 0 63.42
1 0 -1 0 54.56

-1 0 -1 1 55.25
0 0 -1 1 56.49
1 0 -1 1 51.23

-1 0 0 -1 66.86
0 0 0 -1 61.14
1 0 0 -1 48.92

-1 0 0 0 74.24
0 0 0 0 77.16
1 0 0 0 73.58

-1 0 0 1 78.56
0 0 0 1 74.52
1 0 0 1 63.98

-1 0 1 -1 61.00
0 0 1 -1 70.88
1 0 1 -1 74.26

-1 0 1 0 63.05
0 0 1 0 60.53
1 0 1 0 51.51

-1 0 1 1 49.81
0 0 1 1 54.25
1 0 1 1 52.19

mol dm-3 and 1.5 g L-1, respectively. The inhibition effi-
ciency increases with immersion time increase, while the
maximum inhibition efficiency is achieved at the highest
immersion time and the lowest temperature combination.
Fig. 4 shows the 3-D surface plot for the inhibition
efficiency, the temperature and the extract concentration
while the other two factors, the acid concentration and
the immersion time are kept at their mean values of 1.0
mol dm-3 and 5.5, hours respectively. The maximum
inhibition efficiency is indicated at the maximum extract

226
 Odejobi Oludare J., Akinbulumo Olatunde A.

Table 7. Predicted Inhibition efficiencies at 1.5 M HCl.

X1 X2 X3 X4 Y1
(Extract conc) (Acid conc.) (Tempt.) (Time) (% IE)

-1 1 -1 -1 34.72
0 1 -1 -1 42.92
1 1 -1 -1 44.62

-1 1 -1 0 55.25
0 1 -1 0 56.49
1 1 -1 0 51.23

-1 1 -1 1 66.86
0 1 -1 1 61.14
1 1 -1 1 48.92

-1 1 0 -1 49.81
0 1 0 -1 54.25
1 1 0 -1 52.19

-1 1 0 0 63.05
0 1 0 0 60.53
1 1 0 0 51.51

-1 1 0 1 67.37
0 1 0 1 57.89
1 1 0 1 41.91

-1 1 1 -1 48.24
0 1 1 -1 48.92
1 1 1 -1 43.1

-1 1 1 0 54.19
0 1 1 0 47.91
1 1 1 0 35.13

-1 1 1 1 51.22
0 1 1 1 37.98
1 1 1 1 18.24

concentration (2.0 g L-1) and the lowest temperature
(40oC) combination.
Fig. 5 shows the 3-D surface plot for the inhibition
efficiency, the immersion time and the extract concentra-
tion keeping the acid concentration and the temperature
at their mean values of 1.0 mol dm-3 and 55oC, respec-
tively. The inhibition efficiency increases with both the
immersion time and the extract concentration increase.
Fig. 6 shows the 3-D surface plot for the inhibition
efficiency, the temperature and the acid concentration

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 Journal of Chemical Technology and Metallurgy, 54, 1, 2019

Table 8. ANOVA referring to the corrosion rate model.

Source F Value Prob ˃F Significance

Model 76.73 ˂ 0.0001 significant

X1- Extract Conc. 92.24 ˂ 0.0001 significant

X2- Acid Conc. 163.97 ˂ 0.0001 Significant

X3-Tempt 520.87 ˂ 0.0001 Significant

X4-Time 3.56 0.0817 insignificant

X1X2 10.23 0.0070 Significant

X1X3 40.48 ˂ 0.0001 Significant

X1X4 1.10 0.3130 insignificant

X2X3 65.24 ˂ 0.0001 Significant

X2X4 18.93 0.0008 Significant

X3X4 0.0000419 0.9949 insignificant

X12 24.82 0.0003 Significant

X22 36.30 ˂ 0.0001 Significant

X32 126.27 ˂ 0.0001 Significant

X42 0.59 0.4575 insignificant

Lack of fit 25.43 0.0110 significant

while the other two factors, the extract concentration
and the immersion time are kept at their mean values.
The inhibition efficiency decreases with the acid con-
centration increase. The minimum inhibition efficiency
is indicated at the highest acid concentration and the
highest temperature combination. At the lowest acid
concentration of 0.5 mol dm-3, the inhibition efficiency
228
appears to increase with the temperature increase.
Fig. 7 shows the 3-D surface plot for the inhibition
efficiency, the immersion time and the acid concentration
keeping the extract concentration and the temperature at
their mean values. The maximum inhibition efficiency
is indicated at the highest immersion time and the low-
est acid concentration combination. The interactions
 Odejobi Oludare J., Akinbulumo Olatunde A.

Table 9. Optimization Solutions.

S/N Extract Acid Tempt Immersion Inhibition Corrosion Desirability

Conc.(g/l) Conc. (0C) Time (Hr) Efficiency Rate
(M) (%) (mm/yr)
1 1.97 0.50 47.39 4.68 89.785 0.00025 0.940*
2 1.97 0.50 47.50 4.69 89.784 0.00174 0.940
3 1.98 0.50 47.31 4.66 89.784 0.00010 0.940
4 1.96 0.50 47.59 4.72 89.781 0.00193 0.940
5 1.97 0.50 47.26 4.69 89.781 0.05124 0.940
6 1.97 0.50 47.48 4.66 89.781 0.05135 0.940
7 1.98 0.50 47.03 4.71 89.780 0.00040 0.940
8 1.99 0.50 46.99 4.62 89.774 0.00022 0.940
9 1.99 0.50 46.91 4.60 89.768 0.00090 0.940
10 1.99 0.50 46.69 4.75 89.765 0.00118 0.940
11 1.99 0.50 46.83 4.58 89.760 0.00216 0.940
12 1.98 0.50 46.81 4.69 89.757 0.29690 0.940
13 1.95 0.50 47.89 4.74 89.775 0.09337 0.940
14 1.95 0.50 48.06 4.79 89.754 0.00080 0.940
15 1.94 0.50 48.25 4.75 88.742 0.10434 0.940
16 1.96 0.50 47.32 4.96 89.717 0.00187 0.939
17 1.94 0.50 48.22 4.88 89.713 0.00421 0.939
18 1.94 0.50 47.40 4.80 89.672 1.91786 0.939
19 1.93 0.50 47.46 4.72 89.631 2.50183 0.939
20 1.92 0.50 48.42 5.04 89.613 0.16233 0.939
21 1.91 0.50 48.94 4.95 89.608 0.00001 0.939
22 1.93 0.50 47.31 5.41 89.331 0.00050 0.937
23 1.86 0.50 47.30 5.38 89.304 4.60341 0.937
24 1.82 0.50 48.33 5.51 89.098 4.36750 0.937
25 1.87 0.50 51.03 4.17 89.058 0.00227 0.936
26 1.79 0.50 45.51 5.76 88.854 8.36840 0.935
27 1.92 0.50 51.19 4.49 89.568 5.23260 0.932
28 1.67 0.50 45.55 6.19 88.372 9.10636 0.932
29 1.62 0.50 47.01 6.10 88.270 9.94172 0.931
30 1.58 0.50 45.43 6.46 87.974 8.74835 0.929
31 1.57 0.50 46.12 6.43 87.961 8.83162 0.929
32 1.58 0.50 44.32 6.75 87.713 6.60686 0.927
33 1.58 0.50 44.40 6.94 87.488 5.14089 0.926
34 2.00 0.50 48.06 3.07 87.315 0.00053 0.925
35 1.48 0.50 49.16 6.51 87.310 7.04316 0.925
36 1.94 0.50 50.04 3.04 87.233 0.02314 0.924
37 1.45 0.50 44.01 7.00 87.228 3.71783 0.924
38 1.40 0.50 44.22 7.00 87.034 2.87023 0.923
39 1.80 0.50 53.32 3.44 86.990 0.10439 0.922
40 1.33 0.50 43.74 6.89 86.546 1.49273 0.920
41 1.23 0.50 47.21 6.69 85.928 3.36831 0.916
42 1.19 0.50 43.53 6.62 84.725 1.90036 0.906
*Selected optimization results

229
 Journal of Chemical Technology and Metallurgy, 54, 1, 2019
Fig. 8. Plot of Predicted and Actual Corrosion Rate.
of the process variables illustrated by the 3-D surface
plots show that the inhibition efficiency of Euphorbia
heterophylla is dependent on all the variables under
investigation. However, the degree of variation may be
different from one process parameter to the other.
Statistical Analysis and Modeling of the Corrosion
Rate
The ANOVA for the corrosion rate is presented in
Table 8. The table shows a significant model P-value ≤
0.0001. This indicates the significance and the adequacy
of the model. Ten out of the fourteen factor interactions
are significant. The adequacy is also tested by comparing
the model validation parameters. The high R-Squared
value of 0.9880 obtained shows consistency and that the
process parameters explain 99 % of the variance of the
corrosion rate. Pred R-Squared of 0.9043 is in a reasonable
agreement with the Adj R-Squared of 0.9752 because the
difference is less than 0.2. The Adeq Precision of 28.714
indicates an adequate signal. Therefore, this model can be
used to predict the corrosion rate of the process.
A polynomial quadratic regression equation devel-
oped for the corrosion rate and the process variables in
terms of the coded values is given as:
𝑌𝑌2 = 18.92 + 32.56𝑋𝑋1 + 43.41𝑋𝑋2 + 77.37𝑋𝑋3 − 6.40𝑋𝑋4 +
+13.28𝑋𝑋1 𝑋𝑋2 + 26.42𝑋𝑋1 𝑋𝑋3 − 3.36𝑋𝑋1 𝑋𝑋4 + 33.53𝑋𝑋2 𝑋𝑋3 −
−18.06𝑋𝑋2 𝑋𝑋4 − 0.027𝑋𝑋3 𝑋𝑋4 + 15.80𝑋𝑋12 + 19.11𝑋𝑋22 +
of the extract concentration, the acid concentration, the
+35.63𝑋𝑋32 + 2.43𝑋𝑋42
(5)
230
Removing the insignificant factors as indicated in
Table 8 reduces the equation to:
𝑌𝑌2 = 18.92 + 32.56𝑋𝑋1 + 43.41𝑋𝑋2 + 77.37𝑋𝑋3 +
+13.28𝑋𝑋1 𝑋𝑋2 + 26.42𝑋𝑋1 𝑋𝑋3 + 33.53𝑋𝑋2 𝑋𝑋3 −
−18.06𝑋𝑋2 𝑋𝑋4 + 15.80𝑋𝑋12 + 19.11𝑋𝑋22 + 35.63𝑋𝑋32 (6)
Actual and Predicted Corrosion Rates
The experimental data are analyzed to check the
correlation between the values of the experimental and
the predicted corrosion rate and the result of the plot is
shown in Fig. 8. The R2 value of 0.988 shows that the
data points are distributed reasonably near the straight
line. This indicates a good relationship between the
actual and the predicted corrosion rate. The result sug-
gests also that the selected quadratic model is adequate
for predicting the process corrosion rate.
Optimisation of the Process
The forty two optimization results generated by
the numerical optimization technique of Design Expert
8.0.3 are presented in Table 9. The result referring to the
highest desirability of 0.94 (i.e 94 % probability that the
optimisation result is achievable) and the highest inhibi-
tion efficiency is selected.The optimization results show
that the inhibition efficiency of 89.8 % and corrosion
rate of 0.000252 mm/y are obtainable at the combination
temperature and the immersion time of 1.97 g L-1 , 0.5
 Odejobi Oludare J., Akinbulumo Olatunde A.
mol dm-3, 47.4oC, and 4.5 hours, respectively. This result
gives the process parameters combination that provides
the highest inhibition efficiency, a low corrosion rate
and the highest desirability.The optimum inhibition ef-
ficiency reported in this work is higher than the values
of 74.09 % reported by Njoku and Onyelucheya [10] and
that of 74.14 % found by Onukwuli and Omotioma [11].
CONCLUSIONS
The results of this study provide to conclude that
RSM is suitable for modeling, prediction and optimiza-
tion of the inhibition efficiency of Euphorbia heterophyl-
la extract in case of mild steel corrosion in a hydrochloric
acid medium. It is found that Euphorbia heterophylla is
an effective corrosion inhibitor in this case. The extract
concentration, the acid concentration, the temperature
and the immersion time affect the inhibition efficiency
studied. The latter decreases with acid concentration
increase. The optimization results obtained show that an
inhibition efficiency of 89.8 % and a corrosion rate of
0.000252 mm/y are obtained at the combination of values
of the extract concentration, the acid concentration, the
temperature and the immersion time of 1.97g L-1 , 0.5
mol dm-3, 47.4oC, and 4.5 h, respectively.
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