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Soil PH and Soil Acidity PDF
Soil PH and Soil Acidity PDF
Chapter 16
Soil pH is probably the single most informative measurement that can be made
to determine soil characteristics. At a single glance, pH tells much more about a
soil than merely indicating whether it is acidic or basic. For example, availabili-
ty of essential nutrients and toxicity of other elements can be estimated because
of their known relationship with pH.
The term pH was "invented" by the Swedish scientist Sorensen (1909) in
order to obtain more convenient numbers and the idea quickly caught on.
Gillespie and Hurst (1918) seem to have been among the earliest to determine pH
(or PH, as it was then called) electrometrically using a platinum-palladium black-
hydrogen gas electrode, a calomel reference electrode and a fairly cumbersome
potentiometer and galvanometer system. At that period, it was still much more
common to use colorimetric methods with indicator dyes than the electrometric
method.
This changed rapidly, however. Sharp and Hoagland (1919) used a similar
but less involved method than Gillespie and Hurst (1918) and Healy and Karraker
(1922) used a commercially available platinum-hydrogen gas electrode, poten-
tiometer and galvanometer which had been designed by Clark (1920).
The decade of the 1920s saw the development of the quinhydrone electrode
which was less fragile and much less expensive than the hydrogen-platinum elec-
trode. But, it was the development of the glass electrode in the 1930s that brought
the determination of pH very rapidly to its present importance and convenience.
The Beckman Model G pH meter (circa 1931) was practically indestructible and
could be used as a portable as well as a laboratory instrument. Although it was
cumbersome by today's standards, it was virtually foolproof (except for the con-
stantly failing batteries) and many are still capable of operating if not actually
operating today.
As recently as two decades ago, the use of the small, handheld portable pH
meters then available to determine pH in the field was a very imprecise and haz-
ardous undertaking because both electrodes and meters were subject to sudden
failures but this has changed rather abruptly in the last few years. Microcircuitry
and plastic have contributed to rugged pH meters and electrodes that withstand
Copyright © 1996 Soil Science Society of America and American Society of Agronomy, 677 S.
Segoe Rd., Madison, WI 53711, USA. Methods of Soil Analysis. Part 3. Chemical Methods-SSSA
Book Series no. 5.
475
476 THOMAS
considerable abuse and which, in terms of real cost, are very inexpensive com-
pared to the pH meters and electrodes of just a few years ago.
The value of pH as an indicator of soil conditions and the quality of the
equipment now available at reasonable cost make the acquisition of pH data a
fairly simple chore at present. This chapter discusses the methods used, their
strengths and weaknesses and some aspects of interpretation of the data.
DEFINITION OF pH
The concept of pH was derived from the ion product of water, which dis-
sociates very slightly
Kw = [W][OH] =1 x 10-14
at 25°C temperature where H+ and OH- in brackets are activities. When [H+] and
[OW] are equal, each has an activity of (10- 14 )1/2 or (10-7). pH was defined by
Sorensen (1909) as the negative logarithm to base 10 of the hydrogen ion con-
centration, but is now defined in terms of hydrogen ion activity
1
pH = or - log [W] [2]
log [W]
Thus, the pH of pure water would be -log of 1 x 10-7 or 7. As defined, any solu-
tion with a pH below seven is considered acidic, and one with a pH greater than
seven is defined as basic.
Because only dissociated hydrogen ions affect pH, the type of acid that is
present is important in interpreting pH values. Acids are roughly divided into
strong and weak based on their degree of dissociation. Strong acids are almost
completely dissociated (e.g., hydrochloric acid) while weak acids are slightly
dissociated (e.g., acetic acid). In the case of weak acids, the total amount of acid
in solution can be calculated from the pH and the dissociation constant using the
relationship
[3a]
[A-]
PH - pK. = log-- [3b]
a [HA]
(where Ka is the dissociation constant for the acid, [A-] is the activity of dissoci-
ated anion and [HA] is the activity of undissociated acid in solution. Because in
pure acid systems (A-) = (H+), where ( ) refers to concentrations, the negative
log of a weak acid concentration is given by
SOIL pH & SOIL ACTIVITY 477
a
pH = pKap = ~log - - [5]
1- a
When used with soils, pH can aid the investigator greatly in determining
major soil characteristics. Although not adequate as a lime requirement indica-
tor, pH can be used to make a rough estimate of lime requirement and the rela-
tive availability of both P and many of the minor elements (Zn, Cu, B, Mn, Fe,
and Mo, for example). In a more specific way, particular pH values in water can
be used to predict rather well the dominant cations on soil cation exchangers at
the time of soil sampling and analysis. These characteristic pH values are
described below.
CaC03 per hectare is more typical than not of the lime required to control acid-
ity in these cases.
gives a minimum pH value of 3.84 in montmorillonite (Frink & Peech, 1963) and
as the Al3+ becomes small, the pH rises to 4.89 in hectorite (hence the range from
pH 4-5).
Values of pH in this range practically always indicate trouble ahead for
most crop plants because of the negative effects that Al has, especially on plant
root growth (Foy, 1984). Nevertheless, the case is not nearly so serious as that of
free H+ where no plant growth is possible and where costs are very high. In most
cases, the problems of exchangeable Al3+ can be resolved with a few megagrams
of CaC03, a treatment that usually lasts several years and produces economic
increases in crop yields.
Presence of Hydroxy-Aluminum
calcareous soils is strong, normally soils with pH values of 7.6 to 8.3 are found
to be calcareous. Excess CaC03 in the soil immediately indicates that no money
need be spent on lime, that soil acidity will not be a problem and, unfortunately,
that minor elements such as Zn and Fe could prove to be troublesome. On the
whole, the conditions are good but there are some potential problems.
Knowledge of whether a soil is calcareous or not can be especially valu-
able in areas where both calcareous and noncalcareous soils are interspersed on
the landscape. Both soil treatments and expectations will be likely to vary
according to the presence or absence of CaC03.
0.60
0.50
0.40
1
I
<l
Q. 0.30 1 -----
_/--- - /--1-------- ----------·l
0.20
0.10
,
0.00
1: 1 1 :5 1:10
Soil:Water Ratio
Fig. 16-1. The effect of dilution on pH values of California soils showing standard deviation at each
dilution (data from Davis, 1943).
Salt Content
A major factor influencing pH of soils is the salt content of the soil solu-
tion. These salts may be a natural part of the soil such as NaCI, Na2S04 or
Ca(N03)2, or they may be added in the form of fertilizers. In any event, the usual
tendency of the salts is to lower the pH value of the soil progressively as the salt
concentration increases. In acid soils the effect apparently is due to both dis-
placement of AI3+ from the exchange complex and to increased hydrolysis of
various kinds of AI species in the presence of salt (Ragland & Coleman, 1960).
In calcareous soils, an effect of about the same magnitude also is observed
which rather obviously cannot be explained by the same mechanisms. Moore and
Loeppert (1987) relate this reduction in pH to the displacement of Ca2+ from
exchange sites by the salt. At a constant partial pressure of CO 2 of 60.6 Pa
(0.0006 atm), their equation for the pH of a salt-affected calcareous soil is
7
y-O.8269x-O.2936
r'=O.7S24 •
6
•
•
•• •
•• •
U 5
• •
~
c:
•• • •
•• •
J:
Cl. 4 •• •
•••••••• ••
•• •• • •• •••
3 •
•
2
4 5 6 7 8
pH in Hp
Fig. 16-2. A comparison of pH in water and in 1 M KCI for Nigerian soils (data from Okusami et
al.,1987).
in 0.01 M CaClz or M KCI vs. those taken in water. The seasonal effect is basi-
cally a reflection of the loss, formation or accretion of salts during various times
of the year. Under humid conditions, the soil is most nearly free of salts in early
spring due to winter leaching and lack of nitrification. At spring planting season,
the soil is likely to be high in salts due to rapid nitrification and to application f
fertilizer. As crops grow, salts are taken up gradually, lowering the salt content.
But, soon after harvest, the salt level in the soil can be quite high because of the
water deficit, absence of plant uptake, nitrification and mineralization of nutri-
ents in crop residues. Baver (1927) showed that the lowest soil pH occurred dur-
ing June, was nearly equaled in September and that the highest soil pH occurred
in April, generally confirming the scenario given above.
Attempting to deal with problems of variable salt by addition of salts does
not necessarily resolve the problem. As shown in Fig. 16-2, (Okusami et aI.,
1987) the addition of 1 M KCllowers pH about one unit at pH 4 and more than
two units at pH 8, giving still another set of numbers of calibrate mentally with
observed soil conditions.
The approach of Schofield and Taylor (1955) which has been widely used
in England and Canada (Turner et aI., 1963) is to determine pH in 0.01 M CaClz
The resulting difference pH - 1/2pCa has been called the lime potential because
it corresponds to the mean activity of Ca(OH)z. It is somewhat, but not entirely
invariable with naturally changing salt concentration in soils.
Webster and Harward (1959), using both water pH and pH - 1/2 p (Ca +
Mg), showed that the ,.2 (,.2 = proportion of variation explained by the simple
482 THOMAS
The effect of CO2 on the pH of calcareous soils is very large and, given the
variability of the partial pressure of CO2 in the soil atmosphere, it can be con-
sidered the single largest factor affecting the measured pH of calcareous soils.
Bradfield (1942) published data on the pH of CaC03 over a range of Pc~ and
Whitney and Gardner (1943) determined pH on a number of western U.S. soils
as affected by Pc~. Their data for soils are plotted on a graph drawn from
Bradfield's data for CaC03 (Fig. 16-3) and the agreement is excellent. Two soils
dominated by Na2C03 were not plotted because the pH values were so much
higher, but even they had the same slope as the other soils. Figure 16-3 shows
clearly that the reaction
Suspension Effect
The reduction in pH (and the occasional rise) that occurs when the elec-
trodes are placed in the soil suspension rather than the supernatant solution above
the suspension has been called the suspension effect. The interpretations of the
suspension effect basically have been two: first, Marshall (1964) believed that H+
near the clay surface dissociated sufficiently to affect pH when the electrode was
placed near them. In other words, he believed that the pH was truly different in
the soil paste as compared to the supernatant solution. Second, according to
Coleman et aI. (1951), the suspension effect is primarily caused by the effect of
the electrical charge of the soil on the mobilities of K+ and Cl- from the calomel
electrode, rather than the glass electrode. For example, a strongly negative soil
would tend to promote K+ mobility and impede that of Cl whereas, a positively
SOIL pH & SOIL ACTIVITY 483
9.0 .---------------------------------------~
.,...
8.5
•
8.0
7.5
•
:r:a. 7.0 •
•
6.5
•
6.0
•
5.5
5.0 L - -_ _ _ _ _ _ _ _"---_ _ _ _ _...l.-_ _ _ _ _ _- - ' -_ _ _ _ _ _ _ _--'
log Pco,
Fig. 16-3_ The effects of PC02 on pH of calcareous soils (curve from Bradfield, 1942; points from
Whitney & Gardner, 1943).
charged soil (an oxisol horizon, for example) would have exactly the opposite
effect. A soil with very low charge would have very little effect at alL
Although it is generally accepted (Olsen & Robbins, 1971) that the sus-
pension effect is more likely the result of the second explanation (that is, it is
largely spurious), there are some indications that Marshall (1964) was correct
about relative H+ activity on the soil surface as compared with those in the soil
solution. For example, Swoboda and Kunze (1968), based their conclusions on
ionization of weak organic bases, concluded that the surface pH of clays had to
be lower than that of the bulk suspension in order for ionization of the bases to
occur.
Nevertheless, distances a few nanometers from the clay surface have very
little to do with those obtained with a large electrode in a soil suspension.
Perhaps, the emerging field of microelectrodes for pH measurement will shed
further light on the subject.
FUNDAMENTALS OF pH MEASUREMENT
Colorimetric Determinations of pH
pH = pKHI + log -
W]
+ log fI- [7]
[HI]
Electrometric Measurements
In the vast majority of cases, pH is determined using a glass electrode-
calomel electrode system. This is represented by the following diagram
Ej
HgIHgClz, KCI(sat) I test solution Iglass 10.1M Hel, AgClIAg
where the single bars represent phase boundaries and the double bar represents a
liquid junction potential marked Ej. The observed voltage of the cell, E, is pro-
portional to the H+ activity of the solution on suspension and is given by
(E -E')F
pH - -'----'--- [8]
2.303RT
where R is the gas constant, T, the absolute temperature and F is the Faraday con-
stant. At 25°C, this reduces to
(E -E')
pH - -'----"- [9]
0.0591
The term E' includes the potential of the reference (calomel) electrode, the Ag-
AgCI portion of the glass electrode, the asymmetry potential of the glass elec-
trode and the liquid junction potential, E j • When the pH meter is standardized
with a buffer of known pH, the value of E' has been evaluated, and effectively
canceled out. Therefore,
where pH~ is the pH of the standard buffer solution, Es is the voltage at pHs, and
E is the voltage of an unknown solution or suspension (Peech, 1965). This
assumes that the junction potential will not change from the standard buffer to a
soil suspension which, of course, it will as has been discussed earlier.
Equation [10] signifies that, in practical terms, the voltage change for 1 pH
unit is 0.0591 V (or 59.1 mY) at 25°C, and all commercial pH meters are cali-
brated on this basis.
Equipment
There is currently such a proliferation of equipment for determining soil
pH that it is impractical to discuss them all. In general, the electrometer itself
varies in quality with price and the cheaper electrometers cannot be used for
readings more precise than ±0.1 pH unit. For field work they are entirely ade-
quate. For more precise laboratory work they probably are not.
Combination electrodes, which usually have a Ag-AgCI reference rather
than the usual calomel reference electrode, do not give results as accurate as
those obtained with the standard two-electrode system. Nevertheless, for field
work the combination electrodes may be preferable because they are easier to
use. Similarly, plastic-encased electrodes are clearly preferable for field use
because they resist breakage. On the other hand, standard glass electrodes are
much easier to clean between samples and should be more useful in laboratory
applications, unless careless operators are a problem. The new "Ross" electrodes
which use a platinum wire and a redox filler solution to replace the traditional
Ag-AgCl and Hg-HgCI 2/KCI systems have the advantage that the reference is
not sensitive to temperature changes and readings can be made much more
quickly. Their disadvantage is that they cost two to three times as much as con-
ventional electrodes.
Although digital readout is now much more common than the traditional
analog and has many advantages, particularly with indecisive operators, the lat-
ter has the advantage of visually determining the approach of pH to an equilibri-
um value. This can be a very useful feature in certain kinds of studies, such as
titrations.
It should be stated, in general, that the move to solid-state instruments has
eliminated many of the problems of the older machines. On the other hand, many
of those problems (shielding, grounding) could be handled by an experienced
operator. When the new machines fail, they tend to fail completely a require a
return trip to the manufacturer.
Electrode Problems
should be full of solution before use and the vent cap should be open so that flow
can occur. For soils measurements, it usually is preferred to have relatively slow
leakage to minimize contamination of the soil suspension. However if leakage is
too slow, the reading will be in error. The asbestos or glass fiber, or ceramic
opening in the reference electrode (all three are used) may be plugged by KCI
crystals (usually from inside the electrode) or by soil particles on the outside. It
is necessary that some measurable flow occur. This can be checked by filling and
cleaning the electrode and checking that slight wetting occurs.
Determination-pH in water
1. Repeat the above procedure (1-4) but use 0.01 M CaCl2 instead of
water to make the soil suspension.
2. Read pH and record as pHeacl2.
1. Repeat steps 1 to 4 but use 1 M KCI instead of water to make the soil
suspensions.
2. Read pH and record as pHKo .
Use of Microelectrodes
pH Papers
The newer pH papers are reasonably useful for field work is accuracy of
closer than 0.5 pH units is not critical. These papers have maximum practical use
as a first approximation in the field when no pH meter is available. As such they
are helpful in progressive soil mapping programs or in trouble-shooting situa-
tions. Nevertheless, the values usually have to be rechecked using a pH meter
before complete confidence in the results can be attained.
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