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Reading:
General background:
V

 


 
 
Ô

 

à emical Interactions in Soils
 Ôescription of complex
interactions involves
 Mineral à emistry
 àolloidal à emistry
 P ysical à emistry
 Analytical à emistry
 Organic à emistry
 Bioc emistry
 Reactions occur at interfaces

 Solid - liquid
 Liquid - gas
 System is open

 fluxes of water and solutes

 fluxes of gases
 fluxes into biota and from decaying biota
 energy fluxes
 quilibrium vs. Kinetics

 Most soil c emistry is t e study of

reactions at equilibrium.
 T is is OK for prediction of fast reactions
(e.g. ion exc ange and many adsorption
reactions), but soil is mostly a non-
equilibrium system.
 Kinetics
-Dery important for many reactions (e.g.
precipitation and dissolution of most
minerals). Hard to study in a mixed
system like soil.
-Kinetics can be used to describe t e
rates of all reactions but in many cases
t e rates are so slow t at over t e time
of interest t ere is no reaction. Kinetics
in mixed systems can be very complex.
 Soil à emistry and t e Soil Solution

T e soil solution is central to most soil

c emistry
 Soil c emistry is mostly about t e
interaction of ions and molecules in
solution and t eir interaction wit t e gas
p ase and t e solid p ases.
 Most concepts similar to t ose in aquatic
c emistry courses.
Soil Solution Interaction wit ot er
components (Sparks Fig. 4.1)
Inorganic anions and cations in t e soil
solutions (Sparks Table 4.1)
à emical systems in soils
 Properties of t e Elements

 Web Elements as details on t e properties

and be avior of all elements

 Web Elements
ttp://www.webelements.com/
à emical Elements in Soil
 Abundance of t e elements in soils

 Major vs. minor and trace elements

-In geoc emistry and soil c emistry t ese
t e definitions are a bit fuzzy.
 See also plant nutrition literature
-Mostly ³trace´ and ³minor´ are used
interc angeably
-Trace or minor is sometimes defined as
< 1% (10 g kg-1 

Essington says trace is

< 100 mg kg-1
-Some aut ors consider minor as
including ig er concentrations t an
trace
 Major elements

 Major: Al, Si, à, N, Fe, àa, O, K, Ti (P in

plants)

 Remainder are minor (trace) elements

see Table 2.4 in Sparks
j
 Periodicity of t e elements

 Metals
-Group 1 - alkali metals (+I), 1+ ions
-Group 2 - alkaline eart s (+II), 2+ ions
-Transition elements
 Non-metals
-Group 6 c alcogens (- II)
-Group 7 alogens (- I), 1- ions
 Heavy metal??

 It is suc a vague word, t at is often used

incorrectly.

 Is boron a ³ eavy metal´?

 Oxidation states and c arge number

 Oxidation state is indicated by Roman

numerals.
-E.g. Fe(III), Fe(II), Mn(ID), and Mn(II)
 à arge number on an ion.
-E.g. àa2+ not àa+2
 V 





V 
Acids and Bases

See Sparks p. 65
 AàIÔS ANÔ BASES

G Arr enius
G Acid increases H+ concentration
(activity) in solution.
G First and least inclusive definition.
G Base increases OH- activity.
G Brönsted definition - typical definition used
in environmental and soil c emistry
G Acid is a proton donor.
G Base is a proton acceptor
G Includes Arr enius acids and bases
 Brönsted acids and Bases

- Examples

Hàl + H2 O = H3 O + + àl-
acid base conjugate acid conjugate base

NH3 + H2O = NH4+ + OH-

base acid

àH3àOOH + OH- = àH3àOO- + H2O

acid base
 Lewis Acids and Bases

 Lewis Acid ± a broader definition.

(Brönsted definition is subset of t e Lewis
definition)
-Acid is an electron pair acceptor
-Base is an electron pair donor.
- Examples:
- (see Brönsted acids and bases)

e.g. H+ + H2O = H3O+

º
 


 

- H+ is a proton --- can accept a pair of

electrons from one of t e two uns ared
pair of electrons in water to form a
coordinate covalent bond.
[

À
[ [ [ [

-
- water ydronium ion
 Metal ion complexes
- Lewis defines formation of complexes as acid
base reactions.

e.g. Formation of àu2+ amine complex ion.

àu2+ + 2NH3 = àu(NH3)22+

Ammonia as one uns ared pairs of electrons

t at can be donated to empty bonding orbitals
[ in àu2+3

[ [
 Metal ion complexes

 On t e last slide NH3 is a ligand

 T e complex is also called and adduct
(addition product). Not a term used very
muc in environmental c emistry.
 à elation

à elation (multidentate complexes)

 Fe(II) can accept 2 pairs of N electrons
 Bidentate complex
 T is red complex is useful for detection of
reduced Fe.

 

r 
 

 

 

 EÔTA complexes


 [


[
[ 

[ 
[





 [
[ [

[
[


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[ 
[





 
[ [


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|

 N atoms can donate pairs of electrons

 Negatively c arged O atoms can donate
pairs of electrons.
 Negative c arges contribute to ionic bonding
 àan form exadentate complexes
- e.g. àu2+ and ot er first row transition
metal cations.
 àomplexes wit EÔTA can be very strong
† |
 

EÔTA

- Fe ÔTPA, a similar complex is at:

Fe-EÔTA
Systeme International (SI) Units
 Based on mks system

 Basic units; m, kg and s

 Examples:
-àoncentration in a solid, mol kg-1
-Rate of reaction, mol L-1 s-1

 Writing units
- mol L-1 s-1 not mol/L
s
Essington Table 1.5
 Some non SI (derived) units

 We use many units t at are not strictly part

of t e S.I. system
-e.g. L for liter and a. for ectare.
-Land application - kg a-1
 Some equivalences

 Mg m-3 = g cm-3
 mg kg-1 or mg L-1  ppm
 Ëg kg-1 or Ëg L-1  ppb
 c molc kg-1 same as meq/100g
 àonversion of units

 Example: Reporting 5 mg L-1 àa

extracted from a 10 g soil in 200 mL
solution in units of cmolckg-1

   â 
 º        â 

 â 
  º   â 
   â 
    â 


= 0.5 mmolc kg-1

Essington Table 1.6
 In class exercise

- W at is t e common language unit

for g T-1 (gram per ton)?
 Summary

 Soil solution is central to soil c emistry.

 Soil c emistry concentrates on a small
fraction of t e periodic table.
 Knowledge of periodicity is very useful.
 We will mostly use t e Brönsted definition
of acid and bases.
 Will use mostly SI units and a few derived
from S.I