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The document discusses concepts related to pKa values and how they relate to acid dissociation and soil cation exchange capacity (CEC). It explains that pKa values indicate the strength of acids based on the pH at which they are half dissociated. Functional groups in organic matter and clay minerals have different pKa values, determining the pH range over which they contribute most to CEC. When pH equals the pKa, the charged and uncharged forms of these groups are equal.
The document discusses concepts related to pKa values and how they relate to acid dissociation and soil cation exchange capacity (CEC). It explains that pKa values indicate the strength of acids based on the pH at which they are half dissociated. Functional groups in organic matter and clay minerals have different pKa values, determining the pH range over which they contribute most to CEC. When pH equals the pKa, the charged and uncharged forms of these groups are equal.
The document discusses concepts related to pKa values and how they relate to acid dissociation and soil cation exchange capacity (CEC). It explains that pKa values indicate the strength of acids based on the pH at which they are half dissociated. Functional groups in organic matter and clay minerals have different pKa values, determining the pH range over which they contribute most to CEC. When pH equals the pKa, the charged and uncharged forms of these groups are equal.
from neutral compounds; Dissociation = the separation of the ions of an electrovalent compound as a result of the action of a solvent (usually water)
For a weak acid, which dissociates as follows:
HA H+ + A-
An interesting and extremely useful relationship between
pH and pKa can be obtained simply by taking logarithms (to the base 10) of the previous equation: log10Ka = log10[H+] + log10[A- ] - log10[HA] Therefore -log10[H+] = -log10Ka + log10[A-] - log10[HA] Note: log a log b = log (a/b) giving the Henderson-Hasselbalch equation:
The most convenient form of this Henderson-Hasselbalch
equation, is
Using pKa and pH relationship
By using pKa values, we are able to express the strength of an acid (i.e. its tendency to dissociate) with reference to the pH scale. If Ka is large, then pKa will have a low numerical value. E.g., Hydrochloric acid, HCl has a pKa = -3 Acetic acid, CH3COOH has a pKa = 4.77
A strong acid is one which is largely, or
completely, dissociated, and which therefore has a high Ka value (and low pKa). A weak acid is one that is only slightly dissociated in solution, and has a low Ka value.
if we consider the situation where the acid
is one-half (50%) dissociated, or where [A-] = [HA] (that is 50% negatively charged and 50% uncharged) then, substituting in the Henderson-Hasselbalch Equation pH = pKa + log(A-/HA) pH = pKa + log(1) Therefore
pH = pKa + 0
and
pH = pKa
How to use H-H equation
When pH = pKa, the charged and uncharged species have ~equal concentrations. When pH > pKa, the ionized (charged) form is dominant, so there will be more negative sites, therefore, as pH increases, CEC increases
When pH < pKa, the un-ionized, uncharged form
is dominant, so there will be fewer negative sites, thus, as pH decreases, CEC decreases (and AEC increases)
Why care about pKa in soils?
CEC increases as pH increases Early studies showed soil CEC was constant from pH 2.5 5 At pH > 5 the CEC of soil increased, especially in soils containing organic matter or non 2:1 clays
Organic and inorganic components of soil
have functional groups that dissociate at various pHs, leaving them with a negative charge that can attract cations
Acidity of various soil functional groups
Some inorganic surface functional groups are more likely to deprotonate or dissociate than others pKa of Al(OH2)+ = ~5, (Al-OH-Si)+0.5 = ~7, SiOH = ~9.5
2:1 silicate minerals have more Si-OH groups and
contribute less to pH-dependent charge than 1:1 minerals and metal oxides
SOM contributes the most negative charge
85-90% of charge due to deprotonation of COOH and phenolic OH groups which have pKas of 4 6 and 9 - 11