Abstract
A broad variety of materials of biological origin have been successfully used in recent decades for the removal of pollutants from solution. These biosorbents present a range of natural polymers that play a key role on their adsorption capacity. It is therefore critical to understand the physicochemical properties of the chemical groups that form these polymers. According to bibliography, less than 3% of biosorption papers include studies on proton binding. The acid-base properties of biomass are affected by pH, ionic strength and medium composition. Nevertheless, these crucial parameters are not always considered during biosorption studies. This review outlines the major advances on proton binding data interpretation and modelling on biosorbents. In addition, we propose some experimental considerations that cover all issues raised in this review concerning the acid-base properties of biosorbents. Only 30% of the reviewed papers that study algae, agricultural wastes or lignocellulosic materials use Donnan or double-layer surface models to account for electrostatic interactions on proton binding. Expressions for activity coefficients, such as Debye-Hückel or Pitzer equations, are shown only in c.a. 15% of these papers. Moreover, studies investigating a range of ionic strengths represent a 40%, while this variable is not even considered in 20% of the papers. We could not find any biosorption study related to specific salt or Hofmeister effects. Moreover, in 6 out of 10 papers there is important experimental information missing such as the calibration of the electrodes. We consider therefore that there is an important need for reviewing the role of proton binding on biosorption studies.
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- A :
-
Specific surface area
- CA:
-
Condensation approximation
- Ca :
-
Concentration of acid solution
- CA :
-
Total concentration of acidic sites in a biosorbent
- c ± :
-
Ionic distribution at an interface
- E* :
-
Formal potential
- emf, E:
-
Electromotive force
- EXAFS:
-
Extended X-ray absorption fine structure
- F:
-
Faraday constant, 96485.34 C mol−1
- f :
-
Weighted sum of local isotherms
- FTIR:
-
Fourier transform infrared spectroscopy
- (H +)0 :
-
Local proton ion activity at the binding site, e.g. surface proton ion activity
- [H +]0 :
-
Proton ion concentration at the local binding site
- (H +):
-
Experimental accessible bulk activity of the proton ion
- I :
-
Ionic strength
- K ∗ :
-
Stoichiometric proton dissociation constant
- K app :
-
Apparent conditional dissociation constant
- K int :
-
Intrinsic dissociation constant
- K T :
-
Thermodynamic proton dissociation constant
- LFER:
-
Linear free energy relationships
- MSA:
-
Mean spherical approximation
- NICA:
-
Non-ideal competitive and thermodynamically consistent adsorption
- NMR:
-
Nuclear magnetic resonance
- NOM:
-
Natural organic matter
- pK m :
-
Empirical, ionic strength dependent pK
- p(K):
-
Affinity spectrum
- pzc:
-
Potential of zero charge
- Q:
-
Charge of a species net charge
- Q(γ i ):
-
Ratio of activity coefficients of the species in the equilibrium
- SCM:
-
Surface complexation model
- SIT:
-
Specific interaction theory
- U ± :
-
Dispersion-dependent energy term
- v :
-
Volume added in a titration
- V D :
-
Active Donnan volume
- V0 :
-
Initial volume
- WHAM:
-
Windermere humic aqueous model
- XANES:
-
X-ray absorption near edge structure
- X i :
-
Co-ions and counterions
- z i :
-
Charge of a species
- α :
-
Degree of dissociation
- γ ± :
-
Mean ionic activity coefficient
- γ eff :
-
Effective activity coefficient
- γ i :
-
Activity coefficient of species i
- ΔG :
-
Gibbs free energy
- ΔG AB :
-
Lewis acid-base contribution to Gibbs energy
- ΔG ads :
-
Gibbs free energy of adsorption
- ΔG diss :
-
Gibbs free energy in a dissociation equilibrium
- ΔG elec :
-
Electrostatic Gibbs free energy
- ΔG int :
-
Intrinsic Gibbs free energy
- ΔG LW :
-
Lifshitz-van der Waals contribution to Gibbs energy
- ΔG non − elec :
-
Non-electrostatic Gibbs free energy
- θ :
-
Coverage fraction of binding sites
- ρ 0 :
-
Charge in the region occupied by the biosorbent in the absence of mobile ions
- σ :
-
Charge density
- Ψ:
-
Electrostatic potential
- Ψ0 :
-
Electrostatic potential at the binding site
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Lodeiro, P. et al. (2018). A Systematic Analysis and Review of the Fundamental Acid-Base Properties of Biosorbents. In: Crini, G., Lichtfouse, E. (eds) Green Adsorbents for Pollutant Removal. Environmental Chemistry for a Sustainable World, vol 18. Springer, Cham. https://doi.org/10.1007/978-3-319-92111-2_3
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