Published 1996

Chapter 16

Soil pH and Soil Acidity

G. W. THOMAS, University of Kentucky, Lexington, Kentucky

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 ofSoil 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

H20 ... H+ + OH-

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

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

or in a form that is simpler to use

PH - pK. = log --
a

(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

pHA = 2pH - pKa

At a concentration of 1 M, pHA = 0 and pH = 1/2 pKa' so that pH also can be used

to determine the value of pKa in a molar concentration of acid.
In mixed acid-salt systems (buffers), Eq. [3b] can be used to estimate de-gree
of dissociation. A modification of that equation, the Henderson-Hasselbalch
equation, has been used to estimate degree of dissociation in organic matter
(Hargrove & Thomas, 1981) or other pH-dependent exchangers in soil

a
pH = pKap = ~log -- [5] 1- a

(where Kap is the apparent dissociation constant, a is the degree of dissociation,

and ~ is a constant which, for organic matter, and other polyacids generally has a
value of around two). This equation gives the pKap at half neutralization (a = 0.5)
since the log portion disappears and pH = pKap.

SIGNIFICANCE OF SOIL pH VALUES

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.

Presence of Free Acids

Generally, soil pH values in the neighborhood of two to three indicate the
presence of free mineral acid, usually H2S04• A pH value much below 4.0 is
impossible to achieve with Al3+ -saturation so that acidity 10 to 100 times more
intense (pH 2-3) indicates not only the presence of H+ but also a continuing source
of them. A H-saturated soil, prepared from H 2S04 will not persist but will rather
quickly form an AI-soil due to dissolution of the clay minerals by exchangeable W
(Coleman & Craig, 1961). Therefore, a soil with pH of two to three always is found
to have a bountiful supply of free acid. The usual source of this acid is pyritic
minerals which, upon oxidation, form the H2S04. Likely occa-sions where this
excess of acid is found are in mine spoils and recently drained marine sediments,
both of which are frequently well-supplied with pyrites.
The presence of free acid indicates three serious problems: (i) plants will not
grow, (ii) the soil minerals are slowly (or rapidly) being dissolved and (iii) there
will be a high cost of ameliorating soil acidity using lime. In commercial agriculture
this cost most often cannot be met but, for land restoration, where it must be paid, it
can equal the value of the land itself. For example 100 Mg of
478 THOMAS

CaC03 per hectare is more typical than not of the lime required to control acid-ity in
these cases.

Presence of Aluminum Ions

At pH values of four to five, the presence of exchangeable, trivalent Al will be

encountered in mineral soils and, at times even in certain organic soils. The
hydrolysis of both exchangeable and solution Al in Al-saturated montmorillonite
and hectorite,

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

At a pH of 5.5 and above, exchangeable Al3+ is no longer present. Instead, Al

chemistry is dominated by a complex mixture of hydroxy-Al ions, many of them
highly polymerized and virtually nonexchangeable (Rich, 1960).
The smaller particles have a high net positive charge and are true solutes
(Hsu, 1989). These may be involved directly in suppression of root growth (Alva et
aI., 1986). The larger polycations have little direct effect on plant growth but may
strongly affect both P and K availability (Rich, 1964).
In many soils, the major part of the "buffering" region involved in practi-cal
liming is controlled by the hydroxy-Al ions adsorbed on both clay minerals and on
organic matter. From the .standpoint of acidity control in soils, these hydroxy-Al
compounds are very well buffered, indeed, (Coleman & Thomas, 1964) and while
resisting the effect of liming materials, they also resist equally well, the tendency of
acidifying agents (such as NH4- containing fertilizers) to reacidify the soil. They act
about equally well as "sinks" for Wand OH- and, of course, are a major source of the
so-called pH-dependent charge (Thomas & Hargrove, 1984).

Presence of Calcium Carbonate

At the other end of the scale, pH is invaluable as an indicator of excess CaC03

in the soil. Although the effect of the partial pressure of CO 2 on pH of
 SOIL pH & SOIL ACTIVITY

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.

Presence of Sodium Carbonate

When pH values stray towards nine, it can be inferred that CaC03 is no
longer controlling the system and that Na2C03 is assuming control with dire con-
sequences for the long-term health of the soil. When Na2C03 becomes dominant,
not only is Na an important cation on the soil exchangers but Ca ceases to be very
important because of its precipitation as CaC03. In a calcareous soil at normal pH
values of 8.3 or less, Ca in solution is relatively abundant but, as the pH rises
towards nine, CaC03 becomes so insoluble that Na2C03' not CaC03, buffers the
soil. Being a soluble salt, the system is swamped with Na at the expense of Ca.
When the concentrations of the normal salts of Na, such as NaCI or Na2S04 are
relatively low, the combination of exchangeable Na and Na2C03 with low Ca
causes dispersal of the clay and of the organic matter; the result is called black
alkali soils. Fortunately, these soils usually exist as only portions of the land-scape
but, even so, their appearance is a warning of further degradation of the soil in the
future.

FACTORS WHICH AFFECT SOIL pH

The Effect of Dilution

The ratio of water to soil in the suspension has the effect of increasing pH as
the ratio increases. However, the effect is not as straightforward as might be
expected. For example, increasing water content 10 times will not give one pH unit
increase as it would in a solution of acid. Instead, the increase in pH will be only
about 0.4 as shown in Fig. 16-1 from Davis (1943). What is the reason for the
relative insensitivity of suspension pH to dilution?
It appears that, even though pH is a measure of the H+ activity in solution, in
a suspension, the dilution of the soil sample tends to increase the dissociation of H+
from the soil surface and, in addition, to increase the amount of hydroly-sis from
whatever forms of AI might be present. Both effects help to "buffer" the solution
and, therefore, to maintain the pH at a relatively stable value over a wide range of
dilution in acid soils. In soils with higher pH values, hydrolysis of basic cations
tends to maintain a stable pH with dilution. In a practical way, this effect leads to
the conclusion that water/soil ratios are not a highly important factor to consider in
interpreting soil suspension pH values as long as interpretation is based on a
consistent measurement and experience with that measurement.
 480

0.60

0.50

0.40

Q. 0.30
I
<l

0.20

0.10

,
0.00
1: 1
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 CO2 of 60.6 Pa (0.0006
atm), their equation for the pH of a salt-affected calcareous soil is

pH = 6.48 - 0.54 log [Ca2+]

where [Ca2+] is the activity of Ca in the soil solution.
It is worth pointing out also that in tropical soils, there is frequently a ten-
dency for pH values to rise in the presence of salts (Van Raij & Peech, 1972). This
behavior is an indication that salt is releasing more OH- than H+ from the soil or, in
other words, the soil has more sources of positive than of negative charge. This
behavior offers one possibility for the use of both salt and water pH values for the
chemical characterization of the soil. This characterization has value for predicting
the behavior of both sulfate and phosphate as well as the cations that may be present.
 There are two practical problems which have to do with the effect of salt on
pH: the first problem is the seasonal effect first noted by Baver (1927), and the
second problem is the interpretation (or reinterpretation) of pH values taken
SOIL pH & SOIL ACfIVITY

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

regression equation) for the relationship between water pH and percentage

Ca + Mg saturation was slightly better than the ,.z for a similar relationship
between pH - 1/2 P (Ca + Mg) and percentage Ca + Mg saturation. Perhaps
more impor-tantly, their values of l/2p(Ca + Mg) obtained using 0.001 M
CaCl2 showed prac-tically no variation over a range of base saturations from
15 to 150%, good evi-dence that Ca2+ from CaCl2 essentially covered up
any soil differences. This is a clear indication that the extra trouble involved
in determining pH in 0.001 M CaCl2 was not worth the effort.
In summary, even with the problems involved, a soil-water suspension
gives values which can be used with considerable confidence, if not
precision, for making practical field decisions. The use of salts of one kind
or another to correct for variable salts in the soil does not, in general, lead to
better interpreta-tion.

Carbon Dioxide Content

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 P c~. 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

is the major controlling factor which determines pH in calcareous soils.

Naturally, in soils which are dried and ground prior to determining the pH,
the effect of CO 2 should not be so important but where pH is determined
on a fresh sample or in situ, the effect can be very large.

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