Adsorption of Selected Herbicides on Activated Carbon from Single- and Multi-Component Systems—Error Analysis in Isotherm Measurements
Abstract
:1. Introduction
2. Materials and Methods
2.1. Adsorbent and Adsorbates
2.2. Methods and Techniques of Activated Carbon Characterization
2.3. Measurement of Adsorption Isotherms from Aqueous Solutions
3. Results and Discussion
3.1. Adsorbent Characterization
3.2. Error Analysis in Measurements of Adsorption Isotherms from Single-Component System
3.3. Error Analysis in Measurements of Adsorption Isotherms from Multi-Component Systems
A(λ2) = ceq A εA2 + ceq B εB2
4. Conclusions
- The error analysis of the measurements of adsorption isotherms of single substances showed the differentiation in the values of standard deviations of the determined quantities, i.e., equilibrium concentration and absorbance. The largest deviations were obtained for the 2,4-D/RIB system, which confirmed the largest scatter of experimental points on the adsorption isotherm.
- Despite the relatively large dispersion of experimental points of adsorption isotherms, the trend in the adsorption process can be clearly determined depending on the type of adsorbate and the conditions of the adsorption process. This in turn confirms the reliability of the presented results.
- The presence of random errors and the absence of systematic and gross errors were found. The source of random errors was primarily the high inhomogeneity of the adsorbent (variation in grain sizes, physicochemical and structural properties of individual granules) and the method of measuring equilibrium isotherms consisted of the use of many independent adsorbent and adsorbate solution weights. The influence of other variables and factors such as (i) the imprecise preparation of adsorption systems; (ii) instability of external factors during the adsorption process (changes in the form of adsorbate); (iii) inaccurate dilution and measurement of adsorbate solutions; and (iv) the instability of measuring equipment is also probable.
- Significant uncertainties in determining the Freundlich equation parameters m and log K (SDav. = 7–12%) were found.
- The results of equilibrium adsorption studies conducted at different temperatures showed a positive trend in the dependence of adsorption on temperature for the 2,4-D/RIB system (increase in mobility of adsorbate molecules in the solution, wider penetration of the carbon porous structure), and a negative trend for the 4-CPA/RIB system (increase in solubility of the compound, increase in energy of oscillation of molecules enabling desorption).
- In acidic conditions (pH < pKa), the highest adsorption was obtained (mechanism–dispersive interactions between π electrons of the adsorbate aromatic ring and π electrons of the carbon graphene structure). In neutral pH conditions (pH > pKa), a worse adsorption efficiency was observed (mechanism–electrostatic interactions).
- Analysis of the herbicide adsorption (3-CPP) in the presence of an accompanying substance (4-NA) showed a clear decrease in comparison with adsorption from a single-component solution. The adsorption mechanism of the co-adsorbates was strongly competitive in relation to the same active sites placed on the activated carbon surface.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Code | Molecular Weight [g/mol] | Ionization Constant pKa | Solubility [g/L] | Van der Waals Volume [Å3] | Maximal Projection Area [Å2] |
---|---|---|---|---|---|
4-CPA | 186.59 | 3.14 | 0.96 | 149.71 | 56.50 |
2,4-D | 221.04 | 2.81 | 0.68 | 163.66 | 60.90 |
3-CPP | 200.62 | 3.27 | 1.20 | 166.83 | 56.64 |
4-NA | 138.12 | 1.00 | 0.57 | 115.97 | 47.44 |
Carbon | SBET 1 [m2/g] | Vt 2 [cm3/g] | Vmic (t-plot) 3 [cm3/g] | Dh 4 [nm] | Dmo (des. BJH) 5 [nm] | Dmo (HK) 6 [nm] | Dmo (DFT) 7 [nm] | pHpzc 8 |
---|---|---|---|---|---|---|---|---|
RIB | 1052 | 0.65 | 0.46 | 2.5 | 3.12 | 0.66 | 0.57 | 7.8 |
Code | No | m | log K | SD(log a) | SSRg 1 | SSRd 2 | R2 |
---|---|---|---|---|---|---|---|
2,4-D (25 °C) | I | 0.178 ± 0.043 | 2.140 ± 0.552 | 0.087 | 0.131 | 0.113 | 0.537 |
II | 0.241 ± 0.034 | 1.841 ± 0.289 | 0.070 | 0.244 | 0.073 | 0.769 | |
III | 0.184 ± 0.024 | 2.070 ± 0.298 | 0.054 | 0.166 | 0.044 | 0.792 | |
IV | 0.286 ± 0.034 | 1.320 ± 0.179 | 0.057 | 0.222 | 0.048 | 0.822 | |
av. | 0.218 ± 0.025 | 1.621 ± 0.195 | |||||
2,4-D (45 °C) | I | 0.193 ± 0.021 | 2.698 ± 0.322 | 0.058 | 0.283 | 0.050 | 0.850 |
II | 0.259 ± 0.046 | 1.952 ± 0.223 | 0.071 | 0.270 | 0.075 | 0.783 | |
III | 0.202 ± 0.024 | 2.334 ± 0.305 | 0.058 | 0.234 | 0.050 | 0.825 | |
IV | 0.216 ± 0.019 | 2.204 ± 0.214 | 0.045 | 0.261 | 0.030 | 0.896 | |
av. | 0.213 ± 0.017 | 2.295 ± 0.172 | |||||
4-CPA (25 °C) | I | 0.324 ± 0.033 | 1.520 ± 0.168 | 0.052 | 0.261 | 0.040 | 0.866 |
II | 0.205 ± 0.013 | 2.369 ± 0.158 | 0.029 | 0.213 | 0.013 | 0.945 | |
III | 0.223 ± 0.022 | 2.198 ± 0.231 | 0.046 | 0.219 | 0.032 | 0.873 | |
IV | 0.275 ± 0.037 | 1.814 ± 0.263 | 0.065 | 0.236 | 0.064 | 0.786 | |
av. | 0.226 ± 0.021 | 1.989 ± 0.213 | |||||
4-CPA (45 °C) | I | 0.269 ± 0.028 | 1.497 ± 0.437 | 0.062 | 0.139 | 0.058 | 0.707 |
II | 0.210 ± 0.016 | 2.039 ± 0.169 | 0.032 | 0.170 | 0.015 | 0.917 | |
III | 0.191 ± 0.021 | 2.242 ± 0.261 | 0.042 | 0.149 | 0.027 | 0.847 | |
IV | 0.243 ± 0.026 | 1.758 ± 0.201 | 0.044 | 0.173 | 0.030 | 0.854 | |
av. | 0.227 ± 0.020 | 1.880 ± 0.203 | |||||
3-CPP (25 °C) | I | 0.253 ± 0.037 | 1.290 ± 0.207 | 0.076 | 0.273 | 0.082 | 0.769 |
II | 0.318 ± 0.026 | 1.049 ± 0.095 | 0.049 | 0.362 | 0.036 | 0.909 | |
III | 0.187 ± 0.042 | 1.760 ± 0.426 | 0.101 | 0.196 | 0.152 | 0.563 | |
IV | 0.256 ± 0.020 | 1.497 ± 0.128 | 0.045 | 0.325 | 0.030 | 0.915 | |
av. | 0.266 ± 0.022 | 1.233 ± 0.126 | |||||
4-NA (25 °C) | I | 0.356 ± 0.033 | 1.633 ± 0.194 | 0.125 | 1.806 | 0.233 | 0.886 |
II | 0.390 ± 0.041 | 1.504 ± 0.201 | 0.137 | 1.738 | 0.282 | 0.860 | |
III | 0.319 ± 0.034 | 1.849 ± 0.251 | 0.139 | 1.702 | 0.291 | 0.854 | |
IV | 0.314 ± 0.017 | 1.890 ± 0.127 | 0.073 | 1.928 | 0.080 | 0.960 | |
av. | 0.335 ± 0.021 | 1.717 ± 0.122 |
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Blachnio, M.; Zienkiewicz-Strzalka, M.; Derylo-Marczewska, A. Adsorption of Selected Herbicides on Activated Carbon from Single- and Multi-Component Systems—Error Analysis in Isotherm Measurements. Materials 2024, 17, 4232. https://doi.org/10.3390/ma17174232
Blachnio M, Zienkiewicz-Strzalka M, Derylo-Marczewska A. Adsorption of Selected Herbicides on Activated Carbon from Single- and Multi-Component Systems—Error Analysis in Isotherm Measurements. Materials. 2024; 17(17):4232. https://doi.org/10.3390/ma17174232
Chicago/Turabian StyleBlachnio, Magdalena, Malgorzata Zienkiewicz-Strzalka, and Anna Derylo-Marczewska. 2024. "Adsorption of Selected Herbicides on Activated Carbon from Single- and Multi-Component Systems—Error Analysis in Isotherm Measurements" Materials 17, no. 17: 4232. https://doi.org/10.3390/ma17174232