AGRY/NRES 38500 Worksheet #2

Clay Minerals, Organic Matter, & Acid-Base Dissociation Review

Due: Monday 9/19/22 Submit through Bright Space
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PART I. Soil Organic Matter

1. List three reasons why humic substances are important in soils with at least one specifically
related to how a contaminant may interact with soil.

a) Humic substances are important because of the retention of metals and organic chemicals.
This is an important reason especially when it is related to how a contaminant, for example a
metal, interacts with the soil.

b) Buffering which helps the soil to resist change.

3+¿ ,¿
2+¿, Al ¿
c) When humic substances are saturated with H +¿ ,C a ¿
the colloids become denser, smaller,
and more rigid and, they become less susceptible to biological and chemical degradation
which could be caused by a contaminant interacting with soil.

Humic substances can interact with toxics reducing their toxicity, for example, they can reduce
the toxicity of Aluminum (Trevisan et al., 2010).

2. Humic substances are classified into 3 subclasses. Answer the following with the
most appropriate subclass (fulvic acid, humic acid, or humin).

(a) Mid-range molecular weight? Humic acid

(b) More persistent (hardest to degree)? Humin
(c) Soluble in acid and alkaline solutions Fulvic acid
(d) Soluble in alkaline solutions, but NOT in acid Humic acid
(e) Highest degree of polymerization Humin
(f) Highest oxygen content Fulvic acid
(g) Highest cation exchange capacity Fulvic acid

PART II. Soil Minerals

1
 A B

3. Which of the above molecules would be found in the tetrahedral sheet? A

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 AGRY/NRES 385; Lab Worksheet: Clay Minerals, SOM, and pH-pKa

4. (a) Explain the difference between a 1:1 clay and a 2:1 clay using the terms
tetrahedral sheet and octahedral sheet.

The difference is that clay´s 1:1 layer structure includes one octahedral and one tetrahedral
sheet. One example of this is the Kaolinite which has Al3+ in octahedral sheet and Si4+ in
tetrahedral sheets which are bond between the oxygens in the tetrahedral sheet and the
hydroxyls in the octahedral sheet. Meanwhile, about the 2:1 clay, the 2:1 layer structure includes
the union of one octahedral sheet with 2 tetrahedral. One example of this is the Pyrophyllite
which has Al3+ in octahedral sheet and Si4+ in tetrahedral sheet.
(b) Give 2 distinct chemical properties of each of these two types of minerals.

- For the 1:1 clay, it does not have shrink – swell problems and it has a low CEC capacity.
- For the 2:1 clay, differs by isomorphic substitutions and have a high CEC capacity. Some
of them can fix K+.

5. Using the diagram to the right and assuming that the

small blue (or darker for BW print) spheres represent
Al3+ while the larger green spheres represent OH-,
explain whether or not charge neutrality is preserved
for the atoms in the circle.

The charge neutrality is not preserved for the atoms in the

circle because as Al3+ is bond to 6 OH-, the total charge
would be (3)-(6) = -3

6. What is the name of the mineral depicted below and is it a 1:1 or 2:1 clay?

- The name of the mineral is Kaolinite and it is 1:1 clay.

7. If you were to substitute Si4+ with Al3+, what would be the net charge of the clay mineral as a
result of this isomorphic substitution?

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 AGRY/NRES 385; Lab Worksheet: Clay Minerals, SOM, and pH-pKa

- This isomorphic substitution produces a net negative charge.

8. What are the two most important factors contributing to the high reactivity of clays?

The potential of changing the volume and shift in relation to the amount of soil´s moisture and the
amount of Al and Si that is capable of dissolving.

The most important factors are the atomic substitutions in the octahedral and tetrahedral layer and the
potential of changing the volume in relation to the amount of soil´s moisture.

9. Fill in the table by responding to the property denoted in column 1 (and note parenthetical
phrase, e.g., yes/no/NA, range, etc.)

Property Kaolinite Illite Vermiculite Montmorillonite Soil Organic

Matter
(Humus)
Surface area (low, low high Very high Very high N/A
moderate, high or very high)
Cation exchange capacity 5 – 10 cmol 20 – 40 120 - 170 cmol 80-110 cmol kg^-1 200-400 cmol
(representative range) kg^-1 cmol kg^-1 kg^-1 (Uttam,
kg^-1 2014)
pH-depend
capacity for
CEC
Tetrahedral to octahedral yes yes yes yes N/A
sheet ratio (yes/no/NA)
High shrink/swell capacity No No Yes (minimal) yes N/A
(yes/no/NA)
Fixes K+ (yes/no/NA) no yes yes no N/A

PART III. pKa and the pH-pKa relationship

10. (a) Define pKa (e.g., definition analogous to pH)

The level of ionization is described by the pKa and pKa reflects the donation or acceptance of protons
against a pH value. The relation is the next one:

pKa = - logKa

(b)
Write the equation for Ka of a generic acid compound ‘HA’ given the following
reaction:
-
HA  A + H+

k a=¿ ¿

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 AGRY/NRES 385; Lab Worksheet: Clay Minerals, SOM, and pH-pKa

(c)
Assume that the acid HA in (b) above has a pKa of 7.5, calculate the amount of HA
that will exist as an anion at pH = 8 (a pH not unusual of rivers).

pH = p K a + log¿ ¿

1−[ HA ]
8=7.5+log
[ HA ]

1− [ HA ]
log
0.5 [ HA ]
10 =10

[ HA ] ( 3.162 )=1−[HA ]

[ HA ] ( 3.162 ) +[HA ]=1

4.162 [ HA ] =1

1
[ HA ] =
4.162

[ HA ] =0.240

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 AGRY/NRES 385; Lab Worksheet: Clay Minerals, SOM, and pH-pKa

11. Assume a HA as described in 16 above (pK a = 7.5) is a pesticide that has a very
high affinity for soil when in its neutral form (i.e., protonated as HA versus A-)
and thus is unlikely to leach to the groundwater in most agricultural settings
where the typical pH range a healthy agricultural soil is 6-7. However, as an
anion (A-) it has a much higher affinity to be in the water phase. Assuming that
this pesticide is toxic to many fish species, should there be concern regarding
fish livelihood in a nearby river from soil runoff after a heavy rain storm event?
Why?

pH = p K a + log ¿ ¿
7=7.5+log ¿ ¿
−0.5=log ¿ ¿
−¿
A
0.31= ¿
↑ HA

6−7.5=log ¿¿

- According to the previous relations, for the pH range of 6 – 7 is very unlikely to find A−¿¿
which are the toxic species. There shouldn’t be a concern regarding fish livelihood in the
nearby river because the relations are given values under 1 which means that the
predominant specie is HA, which is the one with less affinity to water phase and is
unlikely to leach the groundwater.

12. For an organic base BH+  B + H+ with a pKa = 5.5 :

(a) What fraction of the compound would exist as a cation at pH = 6.5?

6.5−5.5=log¿ ¿

1 B
10 =
B H +¿ ¿

B
10= +¿
BH ¿

B H + ¿=0.1 B ¿

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 AGRY/NRES 385; Lab Worksheet: Clay Minerals, SOM, and pH-pKa

(b) How would this fraction change if the soil pH decreased over time because of
poor management practices?

- If the soil pH decreases over time the fraction would decrease because now the pH value would
B
be smaller than the pKa value so the relation log +¿ could be equal to negative values
BH ¿
and as said, the fraction would decrease in comparation with the fraction of a).

References

Trevisan S, Francioso O, Quaggiotti S, Nardi S. Humic substances biological activity at the plant-soil interface: from
environmental aspects to molecular factors. Plant Signal Behav. 2010 Jun;5(6):635-43. doi: 10.4161/psb.5.6.11211.
Epub 2010 Jun 1. PMID: 20495384; PMCID: PMC3001551.

Uttam, S. (2014). Cation Exchange capacity and base saturation. Retrieved by:
https://extension.uga.edu/publications/detail.html?number=C1040