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CHEMICAL PROBLEMS 2025 no. 2 (23) ISSN 2221-8688
INVESTIGATION OF THE OIL-EMULSIFYING AND OIL-DISPERSING PROPERTIES
OF QUATERNARY AMMONIUM SALTS FORMED FROM TRIETHANOLAMINE WITH HEXADECANOIC AND HEPTADECANOIC ACIDS, AND THEIR APPLICATION
AS ANALYTICAL REAGENTS
Ali Z. Zalov1, Asya F. Shahverdiyeva1'2, Nazani A. Novruzova1, Shahla A. Ibrahimova3
'Azerbaijan State Pedagogical University AZ1000, U. Hajibekova St.68, Baku, Azerbaijan e-mail: [email protected], [email protected] 2Academician Y.H. Mammadaliyev Institute of Petrochemical Processes of the Ministry of Science and Education of the Republic of Azerbaijan, AZ1025, Baku, 30 Khojaly ave. e-mail: [email protected] 3Azerbaijan State Academy of Physical Culture and Sport, AZ 1072, Fatali Khan Khoisky Ave, 98, Baku, Azerbaijan e-mail: shahla. ibrahimova@sport. edu.az
Received 26.09.2024 Accepted 18.11.2024
Abstract: The presented article is devoted to the study of oil-collecting and oil-dispersing properties of the quaternary ammonium salt (DAD), formed by hexadecane (6-DT) and heptadecanoic acid (7-DT) with triethanolamine (TEA) {triethanolammonium salt of hexadecanoic acid (6-DAD) and triethanolammonium salt of heptadecanoic acid (7-DAD)}, as well as its use as an analytical reagent for the extraction-photometric determination of manganese in the form of a mixed-ligand complex (MLC) with 2-hydroxy-5-chlorothiophenol (H2L, L) and DAD in various objects. DAD solutions with a concentration of 0.025%, 0.05%, 0.75%, 0.1% form a colloidal solution in water, and are readily soluble in ethyl and isopropyl alcohols. From a comparison of DADs, it is clear that 6-DAD is superior in its ability to disperse oil in drinking and sea water (6-DAD: Cd=82.2; 7-DAD: 86.2%). 6-DAD exhibited high surface activity, showing a decrease in surface tension from 62.2 mN/m to 34.4 mN/m (andfor 7-DAD from 59.8 mN/m to 33.3 mN/m). DAD was studied as an oil collector and oil dispersant when treating the surface of water that was turbid due to an oil layer 0.17 nm thick. The spectrophotometric method was used to study the complex formation of manganese(II) with L and DAD. The maximum absorption of MLC Mn(II)-L-DAD is observed at X = 545-550 nm (pHop.3.5-5.9). The molar absorption coefficients range from (2.58-2.71) 104. With a single extraction using chloroform, 99.1-99.3% of manganese is extracted as MLC. The optimal conditions for the formation and extraction of MLC are 1.310~3 M L and (1.2-1.5)10~3 M-DAD. Beer's law is followed within the range of 0.2-100 ¡g/mL of manganese. Large amounts ofalkali, AEM, and REE do not interfere with the determination of manganese. The interfering effect of Fe(III) was eliminated using thioglycolic acid or a 20% solution of SnCh, Cu(II) and Cr(VI) were addressed with thiourea, Ti(IV) was treated with ascorbic acid, and Zr(IV), Nb(V), and Ta(V) with fluoride ions. The results of the studies on the formation and extraction of Mn(II) MLC with L and DAD were applied for the extraction-photometric determination of manganese in water.
Key words: manganese, quaternary ammonium salt, triethanolammonium salt of hexadecanoic acid, triethanolammonium salt of heptadecanoic acid, 2-hydroxy-5-chlorothiophenol DOI: 10.32737/2221-8688-2025-2-228-238
Introduction
Like other water basins in the world, the Caspian Sea also has problems with water pollution and, as a result, the deterioration of the environmental situation here. Examples of sources of pollution of this sea are tankers transporting oil, accidents during oil production
and transportation. Characteristic features of pollution by oil and its products are their spills over large water areas, accumulation of sediments on the bottom and pollution of environmental components. Oil spills worsen the quality of water and disrupt the balanced
CHEMICAL PROBLEMS 2025 no. 2 (23)
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connection of the upper layers of water with the atmosphere, causing a disruption in the effect of oxygen on living things [1, 2]. Oil-based substances that reflect sunlight prevent water from absorbing energy. Removal of such stains is especially necessary for the life of marine life, since more than a hundred species of fish live in the Caspian Sea, 95% of the world's sturgeon population [3]. Surface-active substances (SAS) used to remove thin layers of oil from the surface of water are divided into oil dispersants and oil skimmers [4-10].
The concentration of hazardous substances such as chromium, iron, aluminum, manganese, etc., must be below the established standard values [11-14].
The development of modern industrial society creates the need for prompt and reliable control of the content of heavy metals that have toxic properties and inevitably enter the environment. The content of manganese is one of the main indicators in the chemical analysis of natural water. At the same time, an increased concentration of manganese is one of the main reasons for the unpleasant taste of water and the negative impact on human health.
The heteroligand complex of manganese with 1,10-phenanthroline and o-nitrobenzenesalicylic acid has been investigated spectrophotometrically. The method for the extraction-photometric determination of manganese using PAN and xylenol orange is
more sensitive [15]. A method for determining manganese in tap water using sulfosalicylic acid, salicylfluorone, and cetylpyridinium, and in wastewater using 1,3,3-trimethyl-2-[3-(1,3,3-trimethyl-1,3-H-indol-2-ylidene)propenyl]-3H derivatives, has been proposed [15]. Recently, sorption methods have been widely used for trace element determination. Imidazolate framework structures (IFS) attract particular attention as effective sorbents, not only due to their high specific surface area but also due to the feasibility of obtaining them under "mild" conditions [16]. The development of coordination chemistry involves the development of new methods for the synthesis and investigation of coordination compounds, as well as the search for new ligands to obtain compounds with desired properties.
The presented article is devoted to the study of oil-collecting and oil-dispersing properties of quaternary ammonium salt (DAD), formed by hexadecane (6-DT) and heptadecanoic acid (7-DT), with triethanolamine (TEA) {triethanolammonium salt of hexadecanoic acid (6-DAD) and triethanolammonium salt of heptadecanoic acid (7-DAD)} and its use as an analytical reagent for the extraction-photometric determination of manganese in the form of a mixed-ligand complex with 2-hydroxy-5-chlorothiophenol (H2L, L) and DAD in various objects.
Experimental part
Reagents and solutions. In the work, 0.01 M solutions of L and DAD in chloroform were used. The standard solution of Mn (II) (1 mg/l) was prepared by dissolving anhydrous MnSO4 in water containing 1 ml conc. H2SO4, and then diluted to 1 liter with water [15]. The anhydrous salt is obtained from MnSO4 crystalline hydrate by drying at 150°C and subsequent calcination at 400°C. Working solutions with a concentration of 0.1 mg/ml were obtained by diluting the stock solution. To create the required pH value, fixanal HCl (pH 1-2) and acetate-ammonia buffer solutions (pH 3-11) were used. All reagents used were of at least analytical grade.
All the substances used in the work were of analytical reagent grade (a.r.) and chemically pure (c.p.).
Apparatus. The optical density of the organic phase was measured on a KFK-2 (in Russian). Spectrophotometric studies of colored extracts were carried out on a SF-26 spectrophotometer (in Russian).The pH value of the solutions was controlled using an I-130 ion meter (Russia) with a glass electrode. IR spectra were recorded on a Bruker spectrophotometer (Germany).
Method. 0.1-0.8 ml of Mn(II) solution, 2.4 ml of 0.01 M solution L, 2.6 ml 0.01 DAD and 2.8 ml of 1 M HCl solution were added to the test tubes. The volume of the organic phase was brought to 5 ml with CH3O, the total volume was brought to 25 ml with distilled water. After 10 min, the extract was separated and the light
absorption was measured at 540 nm (l = 0.5 cm) in KFK-2.
Determination of Mn (II) in sewage water and bottom sediments. 1L taken for analysis of waste water is evaporated to obtain a precipitate, do not boil. The precipitate was dissolved in 5 ml of HNO3, was transferred to a 50 ml flask and diluted to the mark with water.
General procedure for the synthesis of DAD. For the synthesis of DAD, the reaction of 6-DT and TEA in a molar ratio of 1:1 was carried out under laboratory conditions at 60-70°C (100°C in the case of 6-DT and TEA) for 1 day with intensive stirring. The reaction scheme is as follows:
R-COOH + N(C2H4OH)3 ^ [ R-COO" N+ H(C2H4OH)3] (R = -C15H31, -C16H33)
6-DAD: IR spectrum (KBr) v, cm-1: 3245 (-OH); 2849, 2916, 2954 (-CH); 1466, 1559 (coo-) 2527, 2676 (N+ -H) [17]. Found, %: C 65.1, H 11.6, O 19.7, N 3.6. Calculated, %: C 64.09, H 10.18, 19.04, N 2.97.
7-DAD: IR spectrum (KBr) v, cm-1: 3243 (-OH); 2852, 2920, 2951 (-CH); 1462, 1563 (coo-) 2528, 2673 (N+ -H) [17]. Found, %: C 66.80, H 11.70, O 19.10, N 3.30. Calculated, %:66.03, H 11.25, O 20.09, N 3.16.
The IR spectrum of 6-DAD is represented in Fig. 1.
nnoo .inno mm aaoo 3000 Ml il i ¡¿ckxi 2400 2200 -looa moo 1000 iAoo 1200 100a noo nan
W nvnnumhoi o m - 1
Fig. 1. IR spectrum of 6-DAD.
Study of surface activity and oil-collecting and dispersing properties of DAD.
DAD is an amber-colored solid that freezes at room temperature. Its solutions with a concentration of 0.025%, 0.05%, 0.75%, 0.1%
form a colloidal solution in water, and are readily soluble in ethyl and isopropyl alcohols. The surface activity of DAD solutions of various concentrations at 21°C was determined using a tensiometer at the water-air interface (Table 1).
Table 1. The value of t ie surface activity of DAD at t ie air-water interface (t=21°C)
œ,% 0.00025 0.0005 0.00075 0.001 0.0025 0.005 0.0075 0.01 0.025 0.05 0.075 0.1
a, mN • m-1 6- DAD 62.2 54 50.5 48.2 42.4 39.4 37.5 36.9 34.9 34.7 34.6 34.4
7- DAD 59.8 52 48.5 46.4 41.4 38.2 36.5 35.4 33.9 33.6 33.4 33.3
As can be seen from Table 1, 6-DAD exhibited high surface activity due to a decrease in surface tension from 62.2 mN/m to 34.4 mN/m (and for 7-DAD from 59.8 mN/m to 33.3 mN/m). DAD was studied as an oil collector and oil dispersant when treating the surface of water turbid with an oil layer 0.17 nm thick [18]. The effectiveness of this reagent was studied in laboratory conditions on waters of varying degrees of mineralization using a sample of
Balakhan light oil. The reagent was used both in pure form and as a 5% aqueous solution. A decrease in the area of the initial oil layer due to reagent penetration into oil-contaminated water determines its effectiveness. The oil accumulation coefficient (K) is a value characterizing this effect. K is calculated as the ratio of the initial area of the oil layer to the area of the oil slick formed under the influence of the reagent.
Table 2. Results of studies of oil-gathering and oil-dispersing capacity of DAD
Reagent The state of Distilled water Drinking water Sea water
supply of reagent to the
t, hour K(kd,%) t, hour K(kd,%) t, hour K(kd,%)
oil surface
Undiluted 0 7.6 0 7.6 0 6.0
6-DAD product 1.0-5.0 11.5 1.0-4.0 17.2 1.0-4.0 8.6
(Balakhany 42.0-70.0 15.6 20.0-60.0 8.6 20.0-60.0 Dis.89.0%
oil, thickness 86.0 12.4 84.0 is destroyed 84.0 Dis.79.9%
0.17 mm) 0 6.7 0 6.0 0-4.0 10.1
1.0-42.0 17.6 6.0-20.0 Dis.82.2% 20.0-44.0 Dis.86.2%
5% aqueous 70.0 16.2 44.0 Dis.76.8% 60-84.0 Dis.82.2%
7-DAD dispersion 0 8.2 0 7.8 0-4.0 11.1
(Ramana oil, 1.0-42.0 15.2 6.0-20.0 Dis.72.2% 20.0-44.0 Dis.82.2%
thickness 70.0 10.2 44.0 Dis.76.8% 60-84.0 Dis.76.8%
0.17 mm)
As can be seen from Table 2, 6-DAD water (Kmax=10.1, Kd=86.2%). 7-DAD in the
exhibits oil-accumulating capacity in distilled form of a 5% solution has an oil-accumulating
water in both forms of reagent application. Kmax capacity of Kmax=15.2 mN/m. The reagent
is 15.6 in undiluted reagent form and 17.6 mN/m exhibits a mixed effect as an oil collector-
in the form of a 5% solution. The reagent exhibits dispersant in drinking and sea water (Kmax=7.8
oil accumulation in undiluted product form in and 11.1; Kd=76.8 and 82.2%, respectively). The
drinking water (Kmax=17.2), oil accumulation in reagents retains its effect for 4 days. the first hours in the form of a 5% solution and From a comparison of DADs, it is clear that
oil dispersibility after the 6th hour (Kd=82.2% in 6-DAD is superior in its ability to disperse oil in
the case of the maximum dispersion rate). As an drinking and sea water (6-DAD: CD=82.2; 7-
oil collector-dispersant, the reagent exhibits a DAD: 86.2%). mixed effect in both forms of application in sea
Results and discussion
Charge of the complexes and choice of tetrachloride, benzene, toluene, xylene, iso-
organic solvent. The binary complexes Mn(II)- butanol, and iso-pentanol. Chloroform was found
L, cannot be extracted in chloroform or other to be the most effective.
slightly polar organic solvents. Experiments with The manganese content in the organic
KU-2 and AV-17 ion-exchangers showed that phase was determined photometrically using 8-
these species are charged negatively. oxyquinoline after reextraction, and in the
Electroneutral ternary complexes can be formed aqueous phase - by difference. Based on the
in the presence of DAD. extracted complexes, the distribution coefficient
The following organic solvents were tested (D) and the degree of extraction (R, %) were
for the extraction of these complexes: estimated [15]: chloroform, 1,2-dichloroethane, carbon
[MnU-g 100 xD
u — ttz—^—; K —
'org
Under optimal conditions, chloroform provides degrees of extraction R=99.1-99.3% (Table 3).
Table 3. Optical characteristics, precision and accuracy of the spectrophotometry determination of
Mn(II with L and DAD
Compound pHop. R,% ^max (nm) e-10"4 lgKeq lgP lgKex Working range / |g mL-
Mn-L-6-DAD 3.5-5.8 99.3 545 2.58 8.46 10.34 13.63 0.2-100
Mn-L-7-DAD 3.6-5.9 99.1 550 2.71 8.49 8.91 12.42 0.5-90
Influence of the pH of the Aqueous
Phase. The effect of pH on the formation of Mn(II)- L-DAD complex was studied, in order to find a suitable pH that can be adopted in the determination of cobalt(II) (Fig. 2). The absorbance was found to be maximum in the pH range 1.8-5.8. Extraction of Mn(II) enhanced with the increase in the acidity of the initial
solution; the further increase in acidity lead to the gradual decrease of recovery, which was obviously associated with a decrease in the concentration of the ionized form of L. Probably, it is present in the solution in the nondissociated state. At pH > 7.6, the complexes were hardly extracted, obviously because of the decrease in the degree of DAD protonation.
Fig. 2. Absorbance of mixed-ligand complexes as a function of the pH of the aqueous phase
1- Mn-L-6-DAD, Mn-L-7-DAD CMn(II)= 3.63-10"5M, Cl = Cdad=1.0 10-3 M, X=540 nm, £=0.5 cm
Absorption maxima, reagents concentrations, molar absorptivities, influence of phase volume ratios and effect of time. The absorption maxima of the ternary Mn(II)-L-DAD complexes lie in the range of 540-545 nm (Table I). Complete extraction is achieved at reagent concentrations not lower than 1.3x10-3 mol mL- H2L and (1.2-1.5)x10-3 mol mL- DAD. Mn(II) concentration ranges in which the Beer's law is obeyed are listed in Table 1. The calculated molar absorptivities (smax) belong to the interval (2.58-2.71)x104 Colour develops almost immediately after the reagents addition. The absorbance of the extracts is stable for at least 48 hours. The optimum shaking time is 5 min.
The degree of extraction of M(II) in the form of MLC does not depend on the ratio of the volumes of aqueous and organic phases in a wide
range (from 5:5 to 100:5), which allows for simultaneous concentration and photometric determination of Me(II). Thus, an increase in the volume of aqueous phase 20 times relative to the organic one does not affect the completeness of extraction.
Stoichiometry of the complexes and the mechanism of complexation. The molar ratios of the components of the ternary complexes were established by the equilibrium shift method and the method of Asmus [19]. The results show a complex composition of 1:2:2 (Mn(II):L:DAD). The formation of ternary complexes can be presented in the following way. When manganese interact with two molecules of H2L, they form doubly charged anionic complexes, which are extracted with two molecules of protonated Am. (Fig. 3). Hence, the complexes can be regarded as ion associates between doubly
charged anionic chelates [Mn(HL)2]2- and two protonated Am species: [Mn(HL)2](DADH+)2. The stability constant of Mn(II)-L-DAD complexes was calculated and found to be lgP = 8.91-10.37 at room temperature.
The disappearance of the pronounced absorption bands in the 3200-3600 cm-1 with a maximum at 3460 sm-1 observed in the spectrum of H2L, says that the -OH group is involved in the
formation of the complex. The observed decrease in the intensity, absorption bands in the area 2580 sm-1 shows that -SH group involved in the formation of coordination bond in the ionized state. Detection of the absorption bands at 2380 cm-1 indicates the presence of a protonated DAD [17]. Based on the data obtained, the composition of the extracted complexes can be represented by the formula [MnL2](DADH+)2:
Fig. 3. Determination of the H2L-to-Mn (straight line 1) and the DAD-to-Mn (straight line 2) molar ratios by the mobile equilibrium method. CMn(ii)= 3.63^10'5M, Cl = Cdad=1.010-3 M, SF-26, £=1.0
cm.
o—c2H5
/
C16H33COO"+NH—O—C2H5
O—c2H5
jXKcr
o-
/
-C2H5
C16H33COO+NH—O—C2H5
O—C2H5
o—c2H5
/
C15H31COO"+NH—O—C2H5 \-C2H5
CI
CI
o—c2H5
/
C15H31COO"+NH—O—C2H5 \>-C2H5
Equilibrium constants. Several processes between anionic chelate, [Mn(HL)2]2 , and the
should be taken into account for the system of hydrophobic aminescation, (DADH+)2, with the
[MnL2]2-, (DADH+)2, H2O and CHCI3: equilibrium constants {(AmH+)2[Mn(HL)2]}: I) Association in the aqueous phase
[Mn(HL)2]2-(aq) +2DADH+(aq) ~ [Mn(HL)2](DADH)2 (aq)
[Mn(HL)2](DADH)2
[Mn(HL)2]2-[DADH+)2]
II) Distribution of the complexes between the aqueous and the organic phase
[Mn(HL)2](DADH)2 (aq) ~ [Mn(HL)2](DADH)2 (org) with the distribution constants
_ [Mn(HL)2](DADH)2 (org) D {[Mn(HL)2]2-[DADH+)2]}aq
III) Equilibrium constant (Keq) of the reaction
_ {[Mn(HL)2](DADH)2}(org) _ _
eq {[Mn(HL)2]2-}(aq){[DADH+)2]}aq -
D
KPn =
eq [(DADH)+]2
Where, Ax is the optical density for this - distribution coefficient. Taking logarithm of experiment; Ao - optical density at complete the last expression, we get binding of cobalt ion into a colored complex; D
IgKeq = lgD-21g[DADH+] IV) Extraction of the ternary complexes from water into chloroform
[Mn(HL)2]2- (aq) +2DADH+(aq) ~ [Mn(HL)2](DADH)2 (org) org with the extraction constants
^ex = ^D + P =
{[Mn(tfL)2]2-}(aq){[^Dtf+)2]}aq
The constants of the association p were absorbance values obtained after single
determined by several independent methods: extraction at the optimum conditions (A1) and
Mobile equilibrium method [19,20], Holme- triple extraction (A3): Kd= A1/(A3-A1). The
Langmihr method [19,20], Komar-Tolomachev extraction constants were calculated by the
Method [19,20] and Harvey-Manning method equation Kex= P+ Kd [19,20]. All calculations
[19,20]. The constants of the distribution Kd were carried out at a probability of 95%. The
were determined by comparison of the obtained values are presented in Table 4.
Table 4. Values of the extraction constants (Kex), distribution constants (Kd), association constants _(P) and recoveries (R%) for the Mn(II)-L-DAD-H2O-CH3Cl systems_
Extraction system lsP lgKD lgKeq lgK* R%
Mn(II)-L-6-DAD-H2O-CH3CI 10.18±0.32a 3.45±0.4 9.17±0.82 13.63±0.33e 99.1
10.07±0.84b 13.52±0.31f
10.05±0.57c 13.50±0.39c
10.34±0.72d
8.39±0.41a 3.51±0.4 8.69±0.51 11.90±0.27e 99.3
Mn(II)-L-7-DAD-H2O-CH3CI 8.91±0.62b 12.42±0.53f
8.45±0.35c 11.96±0.18c
8.34±0.19d
Note: aCalculated by the Holme-Langmyhr method [19,20 ; bCalculated by the Harvey-Manning method [19, 20]; cCalculated by the Komar-Tolmachev method [19, 20]; dCalculated by the mobile equilibrium method [19,20]; eCalculated by the formula Kex= Kd+P where is determined by the Holme-Langmihr method [19, 20]; fCalculated by the formula Kex= Kd+P where b is determined by the Harvey-Manning method [19, 20].
Effect of foreign ions (FI) and reagents.
The effect of various ions and reagents on the extraction-spectrophotometric determination of 20 pg Mn (II) is summarised in Table 5. It can be assumed that large amounts of alkaline ions, alkaline-earth ions, NH4+, W(VI), Mo(VI), Cl-, S2O32-, F-, NO3-, SO42-, PO43-, tartrate, citrate, oxalate and tiron; moderate amounts of Cr(VI), Cr(III), Zn(II) and Cd(II); and small amounts of
Mn(II), Sn(II), Cu(II), Al(III), ascorbic acid and SCN- are tolerable. Ni(II), Fe(II,III), V(IV,V), Ga(III), In(III), and Tl(III) interfere seriously at a ratio of 1:1 with respect to Mn(II). However, the interfering effect of some of these ions can be reduced by masking with oxalate, citrate or EDTA (see Table 2). Mn - L-DAD-H2O-CHQ3 system are given in Table 5.
Table ^ 5. Effect of foreign ions on the extraction of 20 pg Mn (II) (n = 6, P =
FI mg FI-to-Mn ratio Mn found R, % FI mg FI-to-Mn ratio Mn found R, %
Citrate3- 5 250 20.03 100.5 Fe(II) 0.5 2.5 19.25 85.0
Oxalate2- 10 200 20.13 102.6 Fe(III) 0.5 2.5 20.90 118.0
Tartrate2- 2.5 250 5.05 101.0 V(IV) 0.05 2.5 20.55 111.0
Ascorbic 0.5 25 5.15 103.1 V(V) 0.05 2.5 19.25 85.0
acid
EDTA 0.5 25 5.10 102.0 Cd2+ 0.2 10 19.86 97.2
CDTA 0.005 0.25 19.73 94.6 Cu2+ 0.06 3 20.17 103.4
Tiron 2.5 125 20.11 102.5 Al3+ 5 250 20.08 101.6
SCN- 0.025 10 20.13 102.6 Zn2+ 0.5 25 20.04 100.8
Cl- 20 100 20.20 104.0 Zr(IV) 3.0 150 20.18 103.5
S2O32- 10 200 19.92 98.5 Nb(V) 0.5 2.5 19.25 85.0
F- 10 500 20.20 104.0 Ti(IV) 2.5 125 20.17 103.4
NO3- 20 1000 20.02 100.3 Ni2+ 2.5 125 19.91 98.2
SO42- 20 500 20.03 100.5 Co2+ 2.5 125 19.91 98.2
PO43- 7 225 20.10 102.0 Cr(III) 1.5 75 19.80 96.0
CIO4- 0.1 0.5 20.73 94.6 W(VI) 5 250 19.88 97.7
NH4+ 20 500 20.02 100.3 Mo(VI) 5 250 19.85 97.0
0.95).
Effect of manganese (II) concentration.
Table 6 shows the calibration characteristics. Compliance with Beer's law was studied by measuring the absorbance value of a number of
solutions containing different concentrations of metal ions. Mn(II) can be determined in the range of 0.2-100 pg /mL (Table 6).
Table 6. Analytical characteristics of some ternary complexes of Mn with L and DAD
Compound Limit of detection: ng •mL-1 Limit of quantification: ng •mL-1 Sandell's sensitivity: ^g- cm-2 Beer's law range fag- mL-1) The equation of calibration curves
Mn-L-6-DAD 15 53 2.30 0.2-100 0.045+0.110x
Mn-L-7- 14 46 2.22 0.5-90 0.056+0.107x
DAD
Table 7 presents data that allow us to that we have developed with some already compare the analytical characteristics of the known ones [15, 21]. photometric methods for determining manganese
Table 7. Comparative characteristics of methods for determining manganese
Reagent [Ref.] pH (solvent) X, nm s10-4 Beer's law range fag mL)
Formaldoxime [15, 26] 10-13 455 1.12 0.7-29
8-mercaptoquinolinate [15,26] 6.0-6.5(CHCl3) 413 0.7 0.8-56
8-hydroxyquinoline [15,26] 7.2-12.5 (CHCI3) 395 0.85 0.2 - 75
1,10 fenantrolin + 2,4- 5.0-11.0 400 0.893 0.15-22.5
dinitrobenzolazosalisil tur§usu [21] (C2H2CI4)
PAN + aniline [22] 2.4-7.0 (CC14) 560 3.95 0.2-120
1-(2-pyridylazo)-2-naphthol and the new reaction with 2-(2- 3.1-5.0 430 2.7 0.2-80
quinolinazo)-5-diethylaminophenol [23]
1,10-phenanthroline and alizarin 5.0-11.0 510 4.2 0.2-60
yellow R [24]
1,10-phenanthroline and 2,4-dinitrobenzenesalicylic acid [25] 5.0-11.0 530 4.0 0.2-110
L-6-DAD 3.5-5.8 (CHCI3) 545 2.58 0.2-100
L-7-DAD 3.6-5.9 (CHCI3) 550 2.71 0.5-90
Analytical Applications. The proposed method (Table 8). The results were compared with the
under the already established optimum well-known methods of formaldoxime [26] and
conditions was applied for the determination of 8-hydroxyquinoline [26] from the literature. Mn(II) in Sewage water and Bottom sediments
Table 8. Determination results of cobalt (II) in the Sewage water and Bottom sediments (n = 6, P = __0.95) __
Compound Analysis object Added, ^g Found, ^g Found in the sample, ^g/kg Sr
- tpS Vn
Mn-L-6-DAD Sewage water Sample 1 2.0 2.45 0.45±0.05 0.06
Mn-L-7-DAD Sample 2 5.0 6.14 1.14±0.11 0.07
Formaldoxime Sample 1 2.0 2.43 0.43±0.09 0.04
8-hydroxyquinoline Sample 2 5.0 6.16 1.16±0.05 0.06
Mn-L-6-DAD Bottom sediments Sample 1 5.0 6.26 1.26±0.05 0.05
Mn-L-7-DAD Sample 2 5.0 6.92 1.92±0.04 0.08
Formaldoxime Sample 1 5.0 6.74 1.70±0.09 0.07
8-hydroxyquinoline Sample 2 5.0 6.25 1.25±0.05 0.05
Conclusions
1. The oil-collecting and oil-dispersing properties of a quaternary ammonium salt (DAD) formed by hexadecane (6-DT) and heptadecanoic acid (7-DT) with triethanolamine (TEA) {triethanolammonium salt of hexadecanoic acid (6-DAD) and triethanolammonium salt of heptadecanoic acid (7-DAD)}, as well as its use as an analytical reagent for the extraction-photometric determination of manganese in the form of a mixed-ligand complex (MLC) with 2-hydroxy-5-chlorothiophenol (L) and DAD in water were studied. DAD was studied as an oil collector and oil dispersant when treating the surface of water that was turbid due to an oil layer 0.17 nm thick.
2. The maximum absorption of MLC Mn(II)-L-DAD is observed at X = 545-550 nm (pHop. 3.5-5.9). The molar absorption coefficients
range from (2.58-2.71)*104. With single extraction using chloroform, 99.1-99.3% of manganese is extracted as MLC. The optimal conditions for the formation and extraction of MLC are 1.3 x103 M L and (1.2-1.5)x103 M-DAD. Beer's law is followed within the range of 0.2-100 pg/mL of manganese.
3. Large amounts of alkali, AEMs, and REE do not interfere with the determination of manganese. The interfering effect of Fe(III) was eliminated using thioglycolic acid or a 20% solution of SnCh, Cu(II) and Cr(VI) were addressed with thiourea, Ti(IV) was treated with ascorbic acid, and Zr(IV), Nb(V), and Ta(V) with fluoride ions. The results of the studies on the formation and extraction of Mn(II) MLC with L and DAD were applied for the extraction-photometric determination of manganese in water.
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