GREEN SYNTHESIS, CHARACTERIZATION, THERMODYNAMIC AND

ADSORPTIVE PARAMETERS STUDIES OF CORROSION INHIBITION

OF MILD STEEL USING SILVER SULFIDE NANOPARTICLES OF
MUSA PARADISIACAL PEEL EXTRACT IN 0.5 M SULPHURIC ACID.

SYLVESTER O. ADEJO1, JOSEPH A. GBERTYO1, VICTOR O. EGBENEJE 1*, SAMUEL E.

OKHALE2, ISAAC OMINYI OGBOGO3 AND OMOLADE OJO4
1
Department of Chemistry, Benue State University, P. M. B 102119, Makurdi, KM 1, Gboko
Road, Benue State, Nigeria.
2
Department of Medicinal Plant research and Traditional Medicine, National Institute for
Pharmaceutical Research and Development (NIPRD), Abuja, Nigeria
3
Department of Chemistry, Benue State University, P. M. B 102119, Makurdi, KM 1, Gboko
Road, Benue State, Nigeria.
4
Department of Chemistry, Federal college of Education (Tech), Gombe State, Nigera

*Corresponding Author:
E-mail: egbenejevictor2018@gmail.com;
Phone: +2348085576834
*Corresponding Author: address: Department of Chemistry, Benue State University, P. M. B 102119,
Makurdi, KM 1, Gboko Road, Benue State, Nigeria.

Abstract

The applications of metals in industrial installations and equipment cannot be overemphasized.

Unfortunately these metals are often attacked by corrosion. Finding corrosion inhibitors that are
environmentally safe and readily available has been a growing trend in the use of natural
products such as essential oils as corrosion inhibitors for metals in acid cleaning processes.
Nanomaterials are rapidly migrating from the laboratory bench into full-scale applications in
many domains including optics, food, alternative energy, medical, environmental remediation,
and chemical engineering and consumer products . This study focuses on the green synthesis of silver
sulfide nanoparticles using aqueous extract of Musa paradisiaca peels as reducing, capping and
stabilizing agents. The synthesized silver sulfide nanoparticles were characterized by Fourier Transform
Infra-red Spectroscopy (FTIR) and UV-vis Spectroscopy. UV-vis spectrum revealed that the synthesized
silver sulfide nanoparticles exhibit a powerful emission peak at 400 nm characteristic of Ag2SNPs
nanoparticle, due to its surface Plasmon resonance absorption band (fig.1) The FTIR spectra reveal the
presence of different functional groups like the alcohol/phenol –OH stretching vibration, carboxylic acid –
OH stretch and N-H stretching of amides. The strong peak at 1620 cm-1 is characterized to alkaene
(fig.2). Weight loss measurement as used by many scholars was used to investigate the inhibitive
properties of silver sulfide nanoparticles prepared from Musa paradisiaca peels extract. The
percentage inhibition efficiency was observed to increase with increase in concentration of
synthesized silver sulfide nanoparticles of Musa paradisiacal peels extract with increase in
temperature fig 1 and 2 at 301K and 313K. From table 1 it can be deduced that there is a
significant difference between the values of %I.E with rise in temperature which is suggestive of
chemical adsorption mechanism. (fig 3 and 4 at 0.1 g/dm 3 and 0.5 g/dm3 respectively). It was
observed that the corrosion rate of the mild steel decreased with increase in concentration and
increase with increment in temperature fig1, 2, 3 and 4. This is also suggestive of chemical
adsorption. Going by the coefficient of determination (R 2) and constants of adsorption isotherm
the adsorption has basic features of chemisorption so it can be modeled by the Tempkin
Langmuir, Freundlich and Adejo Ekwenchi, isotherm.

Key words: Green, nanoparticles, corrosion and characterization

Introduction

The applications of metals in industrial installations and equipment cannot be overemphasized.

Unfortunately these metals are often attacked by corrosion. This attack is usually caused either
by man-made fluids or by one or more natural fluids. Simultaneously these reactions may
damage the metal with consequent loss of cohesive strength [1]. Unlike other natural disaster for
example earthquakes, floods, horrible and weather etc, the economic costs of corrosion are
obviously high and enormous. It can effect and cause hazardous damages to the infrastructure
such as waterways, ports, railroads, hazardous materials storage, clean water, drain systems,
electricity services, automobiles, boats, aircrafts, refining of the petroleum, defense, gas
transmission pipelines and highway bridges. It can also influence the damage of production of
pharmaceutical, petrochemical and chemical materials [2,3]. Corrosion is basically the result of
interaction between materials and their environment leading to the gradual deterioration of
materials. Corrosion being the major industrial problem has attracted a lot of investigators in
recent years [4]. The Great damage caused by corrosion progression have grown into a
problematic of global importance, because of its wastage of very important incomes, product
corruption, efficiency decreasing, expensive repairs, and costly overdesign. Corrosion also
endangers the safety and obstructs the progression of the technology [5]. however, to minimize
corrosion of metals, materials called corrosion inhibitors have been used which can be defined as
a chemical material used to stop or reduce the deterioration of materials (corrosion) when added
to the minerals in very few amounts and do not react with the environmental components. These
substances can be used in any state solid, liquid or gas such as concrete, or paints (as a solid
state), solvents, or aqueous solutions (as a liquid state), and water vapor (as a gaseous state)[6].
Finding corrosion inhibitors that are environmentally safe and readily available has been a
growing trend in the use of natural products such as essential oils as corrosion inhibitors for
metals in acid cleaning processes. The effectiveness of inhibiting corrosion by an essential oil is
closely related for its phytochemical constituents, which includes a non-polar, hydrophobic,
consisting of hydrocarbon molecules and a polar, hydrophilic, which presents one or more
functional groups [7]. These organic compounds can adsorb on the metal surface, block the
active sites on the surface and thereby reduce the corrosion rate. However, synergistic (and
antagonistic) effects are often expected with these mixtures of compounds that may affect their
inhibition efficiency. We have previously reported that the essential oils of many plants are
excellent inhibitors for corrosion of steel in acidic solutions [8, 9].
Nanomaterials are rapidly migrating from the laboratory bench into full-scale applications in
many domains including optics, food, alternative energy, medical, environmental remediation,
chemical engineering and consumer products [10]. silver nanoparticles (Ag-NPs) are one of the
most common and widely used[11]. Previous studies have shown that sulfidation of Ag-NPs can
effectively reduce toxicity. However, the ease with which Ag2S-NPs may transform in some
environments leading to the initial rapid release of dissolved Ag(I) and subsequent formation of
Ag0-NPs suggests that Ag2S-NP is highly safe[12]. Musa paradisiaca is a herbaceous plant (up
to 9 m long) with a robust treelike pseudostem, a crown of large elongated oval deep-green
leaves (up to 365 cm in length and 61 cm in width), with a prominent midrib, each plant
produces a single inflorescence like drooping spike, and large bracts opening in succession,
ovate, 15-20 cm long, concave, dark red in color and somewhat fleshy. Fruits are oblong, fleshy,
5-7cm long in wild form and longer in the cultivated varieties, Several researches have been
carried out on this plant as medicinally and nutritionally potent, traditional anti-diabetic agent
and many other Pharmacological activities[13]. The extract of this plant converted to silver
sulfide nanoparticles which contains many environmental friendly compounds may be utilized as
eco-friendly corrosion inhibitors however this present study seeks to investigate the inhibitive
potential of Musa paradisiaca peels silver sulfide nanoparticles through thermodynamic, kinetic
and adsorptive parameter studies.
MATERIALS AND METHODS

Collection and identification of plant sample

Musa paradisiaca peels were collected from Wurukum market in Benue states Nigeria; the peels
were identified and authenticated at the Department of Biological Sciences, Benue State
University Makurdi by a botanist Mr. Waya.

Plant extraction

Musa paradisiaca peels were oven dried in the chemistry laboratory Benue State University
Makurdi, at 2000C 7 days. The dried Musa paradisiaca peels were crushed and further pounded
into powder using a porcelain mortar and pestle. 20g of the powdered sample was weighed using
electronic weighing balance and transferred in to 800mL conical flask. 200mL of distilled water
was measured using a measuring cylinder and was poured into conical flask containing the
crushed sample. The mixture was boiled for 10 minutes using a heating mantle/hot plate after
which the solution was filtered with the aid of cotton wool and a glass funnel, into a 250mL
conical flask to obtain aqueous extract, which was kept for further analysis.

Green synthesis of silver sulfide (Ag2SNPs) using Musa paradisiacal peels

Green synthesis of silver sulfide nanoparticles were synthesized by reacting silver nitrate with
Musa paradisiaca peels aqueous extract and sodium sulfide at ambient temperature. In this
synthesis, 1g of silver nitrate was dissolved in 100 ml of Musa paradisiacal peels aqueous
extract under magnetic stirring at 270C (room temperature) for 10min. A solution of sodium
sulfide was prepared by dissolving 1g of Sodium Sulfide in 100 mL of distilled water and was
gently swirling for homogeneity. The sodium sulfide solution was then added drop wise to the
solution of AgNO3 and Musa paradisiaca peels extract under continuous magnetic stirring until a
colour of the solution changed to a suspended gray-black color indicating the formation of silver
sulfide nanoparticles[14]. The mixture was centrifuge at 8000rpm for 4 hours, the supernatant
was taken out and the precipitate was collected and rinsed with 5 mL of distilled water. The
obtained nanoparticles were further transferred to a sample bottle for further analysis
Preparation of the coupon
Mild steel rods were purchased and taken to the Department of Mechanical Engineering,
University of Agriculture, Makurdi, Nigeria, where they were press-cut mechanically to form
different coupons, each of dimensions (2 x 1.9 x 0.1) cm with a tiny hole drilled at the edge of
each for the purpose of suspension in the corrodant. The surfaces of the coupons were
thoroughly polished to mirror finish using sand paper, degreased in acetone and preserved in a
desiccator. Subsequently, the initial weights (W i)of the coupons were taken using analytical
weighing balance and then made ready for corrosion studies[15-19].
Corrosion studies
A blank was prepared for the study using 0.5MH2SO4 (50 mL) which acted as the corrodant.
Thereafter, thecoupons as prepared above were individually tied through the tiny hole bored on
the coupons and firmly held by a retort stand at an equal length and uniform spacing, and placed
in various concentrations of silver nanoparticles (1, 2, 3, 4, 5) gdm -3 in 50 ml of 0.5 M H 2SO4.
The corrodant and the inhibitor with the coupons as prepared above were put into the thermo-
stated water bath set at 298k for a period of 6 hours at the constant temperature. After the time
interval the coupons were removed quenched in ammonium acetate, washed in distilled water
and dried in acetone, kept in a desiccator and then the final weight (W f) was taken. The process
was repeated at 308 K. The experiment was performed in triplicate.
Weight loss measurement
The method adopted was that reported by many different scholars [6-10] and weight loss was
represented by equation (1) below,
W =W I −W F (1)
Where is the weight loss of the coupon, W I the initial weight before insertion and W F the weight
after retrieval. Each reading reported is an average of three experimental readings recorded to the
nearest 0.001 g. The inhibition efficiency (IE) was calculated using the formula as represented by
equation (2).

[
% IE= 1−
W1
W2 ]
×100 (2)

where w 1 𝑎𝑛𝑑w 2 are the weight losses (in grams) of mild steel coupon in the presence and
absence of the inhibitor in the acid solution at the same temperature respectively. The degree of
surface coverage, 𝜃, was evaluated by the equation (3) [20-23].
 W1
θ=1− (3)
W2
The corrosion rate of the mild steel coupons was determined for the immersion period from
weight loss using equation (4).
WL
CR ( mgcm h ) =
2 −1
(4)
At
Where, WL is the weight loss in milligrams (mg), A the coupon surface area in cm 2and t the
immersion time in hours. Using an equation similar to the Arrhenius equation (equation 5),
values of activation energy, Ea,were obtained.
Ea
logCR=logA− (5)
2.303 RT
The heat of adsorption Qads was evaluated using equation (6) below.

( ) ()
θ Qads 1
log =LogA + LogK− (6)
1−θ 2.303 R T
where, θ is the degree of surface coverage, R is the molar gas constant, T is the absolute
temperature, and A is a temperature independent factor. Values of heat of adsorption were
θ 1
obtained from the slope (−Q ads−2.303 R ) of a plot of log against .
(1−θ) T
The apparent enthalpy of activation ∆H* and entropy of activation ∆S* values were obtained
through the linearlized form of transition-state theory equation given as thus;

ln ( ) ( )
CR
T
=ln
R
Nh
+
∆ S¿ ∆ H ¿
R
−
RT
(7)

Where h = Planck’s constant

N is Avogadro’s number.
ln CR 1
A plot of ln against will give a straight line and the slope is equal to
T T

( )( )
¿ ¿
∆H R ∆S
and the intercept is equal to ln + ,from where values of ∆H*and∆S* were
R Nh R
calculated.
Value for free energy of adsorption ∆Gads adsorption unto the mild steel surface was
obtained using the equation below;
∆ G ads=−RT ln(55.5 K ) (8)
 θ
Where K=
( 1−θ ) c

C is the concentration of the extract and 55.5 is concentration of water expressed in moles (i.e.
approximately 1000g/dm3) [24].
Langmuir, Freundlich, Temkin and Adejo Ekwenchi, adsorption isotherms (Equation (9-12)
were used to model the adsorption process.

C 1
Langmuir = +C (9)
θ K
−2 αθ
Temkin =LogK + LogC (10)
2.303
Freundlich log θ=LogK +nLogC (11)
1
Adejo Ekwenchi log =log K AE + bLogC (12)
( 1−θ )
where k is the equilibrium constant, C is the concentration of the inhibitor, n is a constant which
tells the intensity of the adsorption process, and have a typical value of 0.6 [24]

Results and discussion

Fig 1 : UV-vis spectral analysis of synthesized AgSNPs from Musa paradisiaca peels extract
Fig 1: FT-IR spectral of synthesized of synthesized AgSNPs from Musa paradisiaca peels
extract
5.00

4.8

4.6

4.4

4.2

4.0

3.8

3.6

3.4

3.2

3.0
%T

2.8

2.6

2.4

2.2
1029.00
2.0

1.8
1602.00 1377.00

1.6

1.4

1.2
3407.00 2925.30

1.00
4400.0 4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 350.0
cm-1

Corrosion studies

Effect of Inhibitor Concentration

The values of weight losses (WL) , inhibition efficiency(%IE), Surface coverage and corrosion
rate for the inhibition of mild steel corrosion by silver sulfide nanoparticle of Musa paradisiacal
peels extrac 0.5 M sulphuric acid at various concentrations and temperatures are presented below
in Table1 and 2 respectively .

Table 1.

Concentratio WL %IE
n 301K (g) 309K 313K 301K 305K 309K 313K
(g/dm3 305K
Blank 0.0548 0.0836 0.1159 0.1678
0.1 0.0393 0.0564 0.0735 0.0989 28.2847 32.5359 36.5833 41.0608
0.2 0.0370 0.0489 0.0628 0.0878 32.4818 41.5072 45.8154 47.6758
0.3 0.0340 0.0374 0.0456 0.0629 37.9562 55.2632 60.6557 62.5149
0.4 0.0292 0.0309 0.0407 0.0531 46.7153 63.0383 64.8835 68.3552
 0.5 0.0230 0.0249 0.0340 0.0389 58.0292 70.2153 70.6644 76.8176

Table 2. Surface coverage and corrosion rate for the inhibition of mild steel corrosion by silver
sulfide nanoparticle of Musa paradisiacal peels at various concentration and temperatures

Concentration Surface Corrosion

(g/dm3) coverage rate
301K 305K 313K 301K mgcm-2h-1 309K 313K
309K 305K

Blank 12.6852 19.3519 26.8287 38.8426

0.1 0.2828 0.3254 0.3658 0.4106 9.0972 13.0556 17.0139 22.8935
0.2 0.32482 0.4151 0.4582 0.4768 8.5648 11.3194 14.5370 20.3241
0.3 0.3796 0.5526 0.6066 0.6251 7.8704 8.6574 10.5556 15.9491
0.4 0.4672 0.6304 0.6488 0.6836 6.7593 7.1528 9.4213 12.2917
0.5 0.5803 0.7022 0.7066 0.7682 5.3241 5.7639 7.8704 9.0046

70 10
9
60
8

Corrosion rate mgcm-2h-1

50
% Inhibition efficiency

7
40 6
5
30 4
Inhibition ef- 3
20 ficiency
2
10
1
0 0
0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55
conc (g/dm3

Figure 1: Variation of corrosion rate (CR) and inhibition efficiency (%IE) of corrosion of mild

steel in 0.5 M H2SO4 at different concentration of AgSNPs from Musa paradisiacal peels at

301K.
 90 25
80
20

corrosion ratemgcm-2h-1
70
%Inhibition efficiency

60
15
50
40
10
30
Inhibition efficiency
20 Corrosion rate 5
10
0 0
0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55
conc (g/dm3)

Figure 2: Variation of corrosion rate (CR) and inhibition efficiency (%IE) of corrosion of mild
steel in 0.5 M H2SO4 at different concentration of AgSNPs from Musa paradisiacal peels at
313K.

Effect of temperature.

The effect of temperature on the corrosion behavior of steel in 0.5 M H 2SO4 containing AgSNPs
from Musa paradisiacal peels 0.1 -0.5 g/dm3 is studied in the temperature range of 301-313 K
using weight loss measurements for 6 hrs. The data of corrosion rates (W) and corresponding
inhibition efficiency (%IE) collected were presented in Table 1 and 2 above. Figure 3 and 4
shows the effect of temperature on the corrosion behavior of mild steel in 0.5 M H 2SO4
containing AgSNPs from Musa paradisiacal peels at o.1 and 0.5 g/dm3 only .
 45 25
40
35 20

corrosion rate mgcm-2h-1

% Inhibition efficiency

30
15
25
20
10
15 Inhibition ef-
ficiency
10 5
5
0 0
300 302 304 306 308 310 312 314
T (K)

Figure 3: Variation of corrosion rate (CR) and inhibition efficiency (%IE) of corrosion of mild

steel in 0.5 M H2SO4 containing 0.1 g/dm3 of AgSNPs from Musa paradisiacal peels at different

temperatures

90 10
80 9 Corrosion rate mgcm-2h-1
70 8
7
% Inhibition efficiency

60
6
50
5
40 Inhibition ef-
ficiency 4
30
3
20 2
10 1
0 0
300 302 304 306 308 310 312 314
T (K)

Figure 4: Variation of corrosion rate (CR) and inhibition efficiency (%IE) of corrosion of mild

steel in 0.5 M H2SO4 containing 0.5 g/dm3 of AgSNPs from Musa paradisiacal peels at different

temperatures
Table 3. Values of activation energy and thermodynamic parameters for silver sulfide nanoparticle of
Musa paradisiacal peels as inhibitor for mild steel corrosion.

Conc. Ea +∆H* ads +∆S* ads +Q ads -∆G ads

(g/dm3 (KJ/mol) (KJ/mol) (KJ/mol) (KJ/mol) (KJ/mol)
301K 305K 309K 313K
Blank 70.9350 68.4242 386.4497 -
0.1 58.3726 55.8535 341.9698 80.0924 13.4867 14.1773 14.8226 15.5058
0.2 54.9555 52.4447 329.8313 39.6729 12.2493 13.3983 14.0249 14.4009
0.3 45.4194 42.9002 296.9079 51.9270 11.8366 13.7756 14.5225 14.5286
0.4 40.2481 37.7289 278.5339 52.8461 12.0175 13.8646 14.2515 14.8436
0.5 36.3239 33.8130 263.8431 50.8357 12.5988 14.1191 14.3595 15.3763

Effects of adsorption parameters

In the present study, the following adsorptions isotherms were used to model the adsorption
process of the inhibitor : Langmuir, Freundlich , Temkin and Adejo Ekwenchi, isotherm.

Table 4. The Adsorption ParametersIsotherm

Langmuir R2 Kad constant -∆Gad

301K 0.850 0.7962 9.4823
305K 0.964 1.0395 10.2847
309K 0.982 0.9542 10.1996
313K 0.959 1.0040 10.4640
Freundlich Ꞃ
301K 0.896 0.6998 0.426 9.1594
305K 0.985 0.9817 0.492 10.1396
309K 0.979 0.9616 0.425 10.2194
313K 0.960 0.9727 0.395 10.3816
Temkin α
301K 0.830 4.3251 -0.4514 13.7183
305K 0.962 6.9984 -0.6318 15.1211
309K 0.969 7.0958 -0.5792 15.3550
313K 0.928 7.6384 -0.5873 15.7455
Adejo Ekwenchi b
301K 0.777 2.5586 0.297 12.4044
305K 0.916 4.2858 0.495 13.8773
309K 0.948 4.4978 0.483 14.1835
313K 0.863 5.3703 0.553 14.8286
 0.7
0.9
0.6
a
f(x) = 0.9962 x + 0.18432
R² = 0.959796820043269 b 0.8
0.7
f(x) = 0.510139028665 x + 0.883722814985
0.5
R² = 0.928375291711517
0.6
0.4
0.5

0.3 0.4
0.3
0.2
0.2
0.1 0.1

0 0
0 0.1 0.2 0.3 0.4 0.5 0.6 -1.1 -1 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2

c 0
-1.1 -1 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 d
-0.05 0.7
-0.1
0.6
-0.15
f(x) = 0.3952614348 x − 0.0126240803 f(x) = 0.5538322688523 x + 0.7299666581728
R² = 0.960682210426816 0.5
R² = 0.863591955203806
-0.2
0.4
-0.25
0.3
-0.3
0.2
-0.35
0.1
-0.4
-0.45 0
-1.1 -1 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2

Figure 5 : (a) Langmuir, (b) Temkin (c) Freundlich and (d) Adejo-Ekwenchi isotherm for the adsorption of
Musa paradisiacal peels extract silver sulfide nanoparticles of mild steel in 0.5 M H2SO4 at 313k
respectively .
Discussions

Synthesis and characterization

A simple method using plant extract reduction has been developed for synthesizing silver

nanoparticles. This methodology could be used for synthesizing a number of metallic

nanoparticles involving other metals with good size and shape morphology [25]. The results

related to the metallic silver sulfide nanoparticles indicates the reduction of silver ions by Musa

paradisiaca peels. Therefore, it can be concluded that the resting cells of Musa paradisiaca peels

can reduce silver ions in their periplasmic space. Initially, the synthesis of silver sulfide

nanoparticles was confirmed by observing the colour change of the reaction mixture. The

appearance of a suspended gray-black color at room temperature suggested the formation of

silver sulfide nanoparticles. The confirmation of formation and stability of the silver sulfide

nanoparticles in the colloidal solution was monitored by using UV-Vis spectral analysis and

FTIR. Ultraviolet-visible (UV-vis) spectra from 200 to 700 nm were measured on a Shimadzu

UV-vis spectrophotometer (UV-3600, Japan). Silver sulfide nanoparticles usually exhibit strong

absorbance in the range of 200-600 nm revealing good photo absorption properties. In Fig 1

below the spectrum revealed that the synthesized silver sulfide nanoparticles exhibit a powerful

emission peak at 400 nm characteristic of Ag2SNPs nanoparticle, due to its surface Plasmon

resonance absorption band [26,27].

FTIR measurements were carried out to identify the possible biomolecules responsible for the

reduction of the silver ions, capping of the bioreduced silver sulfide nanoparticles synthesized by

Musa paradisiaca peels extract filtrate. Representative spectra of nanoparticles obtained from

FTIR measurements manifests absorption peaks located at about 3407.00, 2925.30, 1602.00,

1377.00, 1029.00 cm-1. The FTIR spectra reveal the presence of different functional groups like
the alcohol/phenol –OH stretching vibration, carboxylic acid –OH stretch and N-H stretching of

amides. The strong peak at 1620 cm-1 is characterized to alkaene. It can be deduced and

presume that the flavonoids and terpenoids, which are abundant in Musa paradisiaca, show

characteristic absorption peaks that appear to be responsible for accelerated reduction and

capping process, which give rise to the well-known signatures in the infrared region of the

electromagnetic spectrum (fig 2) [27,28].

Effect of concentration and temperature

The effect of concentration and temperature on the corrosion of mild steel in 0.5M sulphuric acid

using silver sulfide nanoparticles synthesized from Musa paradisiacal peels extract as an

inhibitor was investigated and the results are presented in table 1 and table 2 respectively. Table

1 shows the values of weight loses and percentage inhibition efficiency of the inhibitor at various

concentrations in acid solution. This percentage inhibition efficiency was observed to increase

with increase in concentration of synthesized silver sulfide nanoparticles of Musa paradisiacal

peels extract with increase in temperature fig 1 and 2 at 301K and 313K. The highest inhibition

efficiency of 76.8176% was obtained at 0.5 g dm -3 and the least is 0.2828 % at 301K for 0.1dm -
3
concentrations. From the table 1 above it can be deduced that there is a significant difference

between the values of %I.E with rise in temperature which is suggestive of chemical adsorption

mechanism fig 3 and 4 at 0.1 g/dm3 and 0.5 g/dm3 respectively [29].

Table 2 presents Surface coverage and corrosion rate for the inhibition of mild steel corrosion by

silver sulfide nanoparticle of Musa paradisiacal peels at various concentration and temperatures.

The corrosion rate which was observed to be high in the blank, significantly became reduced as

seen in the corrosion rate upon introduction of the inhibitor into the corroding medium. This

indicates that the synthesized silver sulfide nanoparticles of Musa paradisiacal peels extracts as
an inhibitor can be effectively used to mitigate the rate of corrosion of mild steel in the acid

medium. It was observed that the corrosion rate of the mild steel decreased with increase in

concentration and increase with increment in temperature fig1, 2, 3 and 4. This behavior explains

the fact that the extent of adsorption and the coverage of inhibitor on mild steel surface increases

with inhibitor concentration [30]. The surface coverage area of the synthesized silver sulfide

nanoparticles from Musa paradisiacal peels extracts increased with increased in both

concentration and temperature. This is also suggestive of chemical adsorption [29].

Activation energy and thermodynamic parameters for the inhibition process

The activation and thermodynamic parameters for the inhibition process for the nanoparticles of

silver sulfide synthesized from Musa paradisiacal peels extracts is presented in table 3.

Computed values of activation energy are all positive and significantly lower than that of the

blank as shown in table 3. This implies that inhibition effectiveness increased with increase in

temperature. The dissolution process was also endothermic as the values were all positive. Lower

values of Ea in the presence of inhibitor than in the absence of inhibitor suggest that the process

is chemisorptions while the reverse (higher) is indication of physisorption [24, 31]. The enthalpy
¿
of activation( ∆ H ads ) which is a measure of height of energy barrier that has to be overcome by
the reactant to attain transition state. Computed values of enthalpy of activation are all positive

and lower than that of the blank as shown in table 3 indicating that the efficiency of inhibition

increased with increase in temperature [32, 33]. The dissolution process was also endothermic as

the values were all positive. The average difference 0f Ea – ΔH* was found to be 2.55KJMol -1

and is equal to the value of RT (R is the universal gas constant and T is the average of the

temperature) at which the studies was conducted. This implies that the corrosion process of the
 ¿
metal in acid medium is unimolecular reaction [34]. The entropy of activation ( ∆ S ads ) values for

the inhibitor is highlighted in Table 3 also. The shift towards positive value of entropies (S *)

implies that the activated Complex in the rate-determining step represents dissociation rather

than association, meaning that disorderliness increases on going from reactants to the activated

complex [35, 36].

The heats of adsorption( Qads ) for all inhibitors were all positive indicating that the processes were

endothermic. This means absorption of energy from the surrounding was required for the

reaction to be sustained [37].

The values of Gibbs free energy of adsorption ( ∆G ads ) in aqueous solution are usually around -20

KJ mol-1 or lower (more positive) which indicate that the adsorption is due to electrostatic

interaction between the inhibitor and metal (physisorption). While those around or higher (more

negative) than -40 KJ mol-1 involve charge sharing or transfer of electrons between the molecules

and metal (chemisorption) [38, 39]. The ΔGad values presented in table 3 are all negative and

increase with rise in temperature indicating spontaneity of adsorption process and stability of

below -20 KJ mol-1or slightly above -20 KJ mol-1 which signifies that the reaction is physical

adsorption mechanism [40].

Adsorption isotherm for the inhibition process

The mechanism and action of inhibition has been attributed to their adsorption process of the

adsorbate (inhibitor) unto the surface of the metal (adsorbent); hence adsorption isotherm models

have been extensively used in its confirmation. In the present study, the data obtained from

weight loss method were fitted into the various two-parameter isotherm going by the coefficient
of determination (R2) and the fitted into the : Langmuir, Freundlich , Temkin and Adejo

Ekwenchi, isotherm.

(a) Langmuir Isotherm: Langmuir isotherm adsorption is usually an indication of

monolayer coverage of inhibitor on the surface of mild steel. The slopes and intercepts

are given in table 4 along with the coefficient of determination (R 2) for nanoparticles of

silver sulfide synthesized from Musa paradisiacal peels extracts . An ideal Langmuir

isotherm plot should have a good R 2 value and intercept of zero (fig. 5a) with a positive

adsorption equilibrium constant k [41].Langmuir Isothermis give below

C 1
= +C (9)
θ K

In reference to the values of regression coefficient R 2 as highlighted in the table 4, the

adsorption equilibrium constant k value are positive and intercept zero indicative of

suitability of the Langmuir isotherm to the adsorption behavior of inhibitors. Langmuir

isotherm is applicable to both physisorption and chemisorptions. Hence Langmuir

isotherm can be used to model the adsorption of this studies.

(b) Temkin Isotherm: The Isotherm constant and coefficient of determination of (R 2) are

presented in table 4 and fig. 5b, the constant α which is related to the heat of adsorption,

equally increase with increase in temperature, which is a characteristics of

chemisorption. Examination of the data shows that the Temkin isotherm is applicable to

the inhibitor adsorption on mild steel and the adherence of this adsorption layer species.

The negative values of “α” are indication of repulsive interaction in the absorbed layer,

the increase in the value of ΔGads with rise in temperature is a feature of chemical
adsorption [40]. The adsorption has basic features of chemisorption so it can be modeled

by the Tempkin Isotherm which is given as:

−2 αθ
=LogK + LogC (10)
2.303

(c) Freundlich Isotherm: The Freundlich constant has to do with the adsorption

intensity and the heterogeneity of the material, and its good value should be close to 0.6

[42]. The values of the parameter nf obtained were not close to 0.6 The fact that the

obtained average value of n, obtained is 0.4345, and is below 1 suggests that this

adsorption process can reasonably be modelled by this isotherm on normal

adsorption[43,44]. Values of regression coefficient R 2 is highlighted in the table 4 and

fig.5c

AdejoEkwenchi Isotherm: Values of regression coefficient R2 of Adejo-Ekwenchi

Isotherm can be seen in the table 4 and fig.5d. Adejo-Ekwenchi Isotherm as it seems to

be obeyed by nearly any adsorption process, it is centered on the fact that for any

adsorption process, the available surface of a given quantity of the adsorbent decreases

with increase in the concentration of the adsorbate; hence the different between the total

available surface on the adsorbent and the fractional surface coverage decreases with

increase in the adsorbate concentration (i.e the more the surface coverage the less the

available surface). Therefore, there exist an inverse relationship between the available

surface and concentration of the adsorbate [32]. Decrease in b value with rise in

temperature signifies physisorption, while increase or fairly constant value indicates

chemisorptions. From the table 4, it is obvious that the absorption of the inhibitors onto

the metal surface is chemisorptions as b increases with temperature or fairly constant.

Adejo Ekwenchi isotherm is expressed as

 1
log =log K AE + bLogC (12)
( 1−θ )

Conclusion:

The use of green approach in the synthesis of nano materials has attracted significant attention in

order to protect environment from hazardous wastes. However the importance in the use of

benign approach in the synthesis and development of nanoparticles through the fast, eco-friendly

and convenient method cannot be overemphasized. A simple method using plant extract

reduction has been developed for synthesizing silver nanoparticles. This methodology could be

used for synthesizing a number of metallic nanoparticles involving other metals with good size

and shape morphology [25]. The results related to the metallic silver sulfide nanoparticles

indicates the reduction of silver ions by Musa paradisiaca peels. Therefore, it can be concluded

that the resting cells of Musa paradisiaca peels can reduce silver ions in their periplasmic space.

Initially, the synthesis of silver sulfide nanoparticles was confirmed by observing the colour

change of the reaction mixture. The appearance of a suspended gray-black color at room

temperature suggested the formation of silver sulfide nanoparticles. The confirmation of

formation and stability of the silver sulfide nanoparticles in the colloidal solution was monitored

by using UV-Vis spectral analysis and FTIR. From the above results, it has been shown that

silver sulfide nanoparticle of Musa paradisiaca peels extract shows to be a good inhibitor which

can be used when develop to mitigate the rate of corrosion since it is environmentally benign as

this will greatly enhance global sustainability.

Acknowledgement
We are grateful to our university management: Benue State University, Makurdi; for providing

the enabling environment for the successful research. Our gratitude also goes to the staff of

Biological Sciences and Chemistry laboratories of our great institution for their help and support

that has brought the research to this end.

Conflict of interest: the authors declare no conflict of interest.

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