Published 1965

60 Hydrogen-Ion Activity

MICHAEL PEECH
Cornell University
Ithaca, New York

60-1 INTRODUCTION

The determination of the hydrogen-ion activity or pH of soils is by far the

most commonly made soil test. It is wiOely used by soil testing laboratories
and county agents for estimating the lime needs of soils.
Sorensen (1909) defined pH as the negative logarithm of the hydrogen-
ion concentration. Inasmuch as hydrogen-ion activity rather than hydro-
gen-ion concentration is actually measured by potentiometric methods, the
pH is more correctly defined by the following equation:
pH = -log aH+ = -log CH+fH+ [IJ
where the ion activity coefficient fH+ is usually assigned on the basis that
fK+ = fCl- for potassium chloride solutions at all concentrations or that
fH+ = fCl- = f ±HCl (McKinney et aI., 1947). Because single-ion activity
coefficients cannot be determined, the National Bureau of Standards (NBS)
has certified a series of buffer substances from which standard buffer solu-
tions of known pH values can be readily prepared. The NBS standard pH
scale is calibrated in terms of these standard buffer solutions (Bates, 1954;
Willard et aI., 1958).
The convention of expressing the hydrogen-ion activity as the negative
logarithm has been widely adopted for convenience to avoid the awkward
use of decimals or exponents, but there is another important advantage in
using the pH scale for estimating the lime requirement of soils. It can be
seen from Fig. 61-1 that, within the pH range from 4.5 to 6.5, there is a
linear relationship between the soil pH and the percent of base saturation
of the soil. Thus, within this pH range, the final pH of a given soil should
increase linearly with the amount of limestone incorporated into the soil.
Also within this pH range, the observed pH value of a composite soil sam-
ple, consisting of a number of soil cores, may be estimated more accurately
by the arithmetic average of the pH values of the individual cores than by
the pH value derived from the arithmetic average of the hydrogen-ion ac-
914
60-1 INTRODUCTION 915

tivity of the individual cores. This observation should then justify the com-
mon practice of calculating arithmetic averages of soil pH values obtained,
for example, on different plots representing the same soil type.
Methods for determining soil pH may be divided into two groups:
colorimetric and electro metric. The colorimetric method (Clark, 1923;
Kolthoff and Laitinen, 1941) makes use of suitable dyes or acid-base indi-
cators, the color of which changes with the hydrogen-ion activity. Use of
the colorimetric method is now primarily confined to field test kits which
are capable of giving results that agree within 0.3 pH unit with those given
by the electrometric method (Mason and Obenshain, 1939).
In most colorimetric techniques, the pH of an aqueous soil extract is
usually measured. Woodruff (1961), however, has recently proposed a
colorimetric method based on measurement of the pH of a O.OlM CaCl2
extract of soil in attempt to fix the salt concentration of the soil and thus
minimize the variation in soil pH due to fluctuation in the amount of
soluble salts (cf. section 60-2.2).
Acid-base indicators behave like weak acids or weak bases and show
different colors in undissociated and dissociated forms. The dissociation of
an indicator acid may be represented by
HI
(acid
~ H+ + 1- [2J
(alkallne
color) color)

The color of the indicator is determined by the relative concentrations of the

acid HI and the basic 1- forms and thus varies with pH in accordance with
the following equation:

pH = pKHI + log U:J

[HIJ + logj1- [3J
in which pKHI is the negative logarithm of the dissociation constant of the
indicator and f1- is the activity coefficient of the indicator ion. Two solu-
tions having the same hydrogen-ion activity or pH as measured electromet-
ric~lly will impart the same color to an indicator only if their ionic strength
is the same because the ratio of the concentrations of the two forms of
indicator will be the same only if the activity coefficient, fI-, is the same in
both solutions. In the determination of pH of saline soils, the salt error may
be very large indeed. The following corrections (Kolthoff and Laitinen,
1941) for the three indicators, commonly employed in colorimetric meas-
urement of soil pH, would have to be subtracted from the observed pH of a
soil extract having an ionic strength of 0.5 (e.g., O.sM NaCl) when com-
parison is made with a buffer solution having an ionic strength of 0.005;
bromocresol. green, 0.34; chlorophenol red, 0.34; and bromothymol blue,
0.40.
Another common source of error in the colorimetric determination of pH
arises from the use of indicators in organic solvents or alcohol-water mix-
tures. Addition of alcohol to an aqueous solution containing an indicator
916 HYDROGEN.ION ACTIVITY

decreases the ionization constant of an indicator acid and thus shifts the
color-change interval of the indicator toward higher pH values (cf. equa-
tion [3]) . Hence, a deep yellow color shown by bromothymol blue in alcohol
does not necessarily indicate the presence of an acid in the alcohol. For the
same reason, indicators that are made up in alcoholic solutions should not
be used in field pH test kits in which the indicator solution is allowed to
come in direct contact with the soil.
In the electrometric method (Bates, 1954; Willard et aI., 1958), the
potential of a hydrogen-ion-indicating electrode is measured potentio-
metrically against some reference electrode, which is usually a saturated
calomel electrode and which also serves as a salt bridge in forming a liquid
junction between the saturated KCI and the test solution. When contamina-
tion of the test solution with either the K + or the CI- would be objectiona-
ble, a salt bridge of NH4Cl or KNO a may be interposed between the calomel
electrode and the test solution.
The glass electrode has largely supplanted the other indicator electrodes
that are reversible to hydrogen ions because of rapid advances that have
been made in construction of sturdy glass electrodes and suitable vacuum-
tube potentiometers or pH meters. The glass electrode-calomel electrode
assembly may be represented by the following cell:
E;
Hg I Hg2Cb, KCI (Sat.) II test solution I glass I O.lN HCI, AgClI Ag [A]
where a single vertical line indicates a phase boundary, and where a double
vertical line indicates a liquid junction potential, which in the above cell is
also marked as E j • The observed electromotive force of such a cell E is a
function of the hydrogen-ion activity of the solution and is given by
_ (E - E')F
pH - 2.303RT [4]
or,
(E - E') 0
pH = 0.0591 at 25 C. [5]

in which the symbols R, T, and F represent the gas constant, the ab-
solute temperature, and the faraday, respectively; and E' includes the po-
tential of the reference electrode (calomel electrode), the internal electrode
(Ag-AgCI electrode), the "asymmetry potential" of the glass electrode, and
the liquid junction potential E j • Setting the slidewire or the indicator needle
of the pH meter to the pH of the standard buffer solution is equivalent to
evaluation of the constant E' in equations [4] and [5]. From equation [4],
it may be shown that,
(E - E.)F
pH = pH. + 2.303RT [6]

in which pHs is the assigned pH of the standard buffer solution, and E and
60-2 FACTORS AFFECTING SOIL pH 9 17

E. are the observed values of the electromotive force (emf) of the cell
when the electrodes are immersed in the unknown solution and the standard
buffer solution, respectively. Equation [6] constitutes the operational defini-
tion of pH (Bates, 1954). It is tacitly assumed that the liquid junction po-
tential remains unchanged when the standard solution is replaced by the
unknown solution.
The cause as well as the magnitude of the liquid junction potent~al Ej,
shown in Cell [A], in clay and soil suspensions has been the subject of much
discussion (Jenny et aI., 1950; Coleman et aI., 1951; Peech and McDevit,
1951; Peech et aI., 1953; Raupach, 1957).Peechetal. (1953) have shown
that the sign of E J in Cell [A] is positive (i.e., the suspension is charged
positively with respect to the saturated KCI solution) in suspensions of clays
and soils saturated with monovalent cations and is negative in suspensions
of clays and soils saturated with bivalent cations. Thus in most soils the sign
of E j is negative and of sufficient magnitude to lead to a negative suspension
effect, i.e., the apparent activity of hydrogen and other cations is higher in
the equilibrium solution (dialyzate) than in the clay or soil suspension.
These findings have been fully confirmed by Raupach (1957). To avoid
the errors due to the peculiar nature of the liquid junction potential in clay
and soil suspensions, Peech et al. (1953) have recommended that the
saturated KCI salt bridge (or the calomel electrode) be placed in the clear
supernatant liquid and that the glass electrode be preferably placed in the
settled suspension after the clay particles have settled out from the suspen-
sion. Under such circumstances, the pH of the clear supernatant equilibrium
solution will be measured rcgardless of the position of the glass elcctrodc.
Because of the poor buffer capacity of the clear supcrnatant solution, how-
ever, it is better to place the glass electrode in the partly scttled suspension.

60-2 FACTORS AFFECTING SOIL pH

60-2.1 Effect of Dilution

Thcre has becn little agrcement among different invcstigators as to the

proper ratio of soil to watcr that should be uscd in preparation of the soil
suspension for pH measurement. Within the entire range of soil water con-
tent from the moisture equivalent to the soil-to-water ratio of 1: 5, the
effect of dilution is to increase the pH of the soil suspension, regardless of
the initial pH value of the soil or the distilled water used in preparation
of the suspensions. The increase in pH upon dilution from the "sticky
point" to a soil-to-water ratio of 1:5 may bc over 1 pH unit (Chapman
et aI., 194 t; Huberty and Haas, 1940; Snyder, 1935). A soil-to-water ratio
of 1: 2.5 was adoptcd in 1930 by the Soil Rcaction Committee of the I ntcr-
national Society of Soil Sciencc, whcrcas at: t ratio has becn adopted in
918 HYDROGEN.ION ACTIVITY

several states (Peech et al., 1947). Since the introduction of the more rugged
type of glass electrodes suitable for measuring pH values of soils at very
low water content, the trend has been toward use of narrower ratios, e.g.,
sticky point and saturated soil paste. Davis (1943) has correctly cautioned
against pH measurements at soil moisture contents below the moisture
equivalent because of errors due to poor contact between the soil and the
glass electrode as well as to high soil resistance which may yield an extra-
neous electromotive force in the grid circuit with certain types of vacuum-
tube pH meters. There is even a more important source of error in the
measurement <?f pH of soil suspensions and especially of soil pastes due to
the liquid junction potential discussed in the preceding section.

60-2.2 Effect of Soluble Salts

The pH of a soil suspension decreases with increasing concentration of

neutral salts, e.g. NaCI, CaSO" in the suspension. The increase in pH of a
soil suspension upon dilution is thus a direct corollary of the observed
decrease in pH of the suspension upon addition of neutral salts. The pH
value of many soils undergoes periodic variation (Baver, 1927; Carolus and
Lucas, 1943; Snyder, 1935), being lowest during the hot and dry season
and highest during the cool and rainy season. This seasonal variation in
pH value of soils as measured in aqueous suspensions appears to be closely
associated with fluctuations in amounts of soluble salts, such as sulfates and
nitrates, which accumulate during the dry periods and thus lower the pH
of the soil, but which are subject to leaching during the rainy season, when
the pH returns to its maximum value. Some of this seasonal variation in the
amounts of soluble salts present in the soil is, of course, due to addition of
fertilizer salts.
Because the pH values in IN KCI solution are less influenced by changes
in biological and meteorological conditions and thus reflect a more intrinsic
characteristic of the soil than the soil pH values measured in water, many
European workers prefer to measure the pH of soils in IN KCI (Puri and
Asghar, 1938). The pH value of many soils in IN KCI, however, may be as
much as 1.5 to 2.0 pH units lower than that measured in aqueous suspen-
sions using the same soil to water ratio. With this high concentration of salt,
the measured pH is also markedly influenced by the soil: solution ratio.
More recently, Schofield and Taylor (1955) have proposed a method for
the determination of soil pH in O.OIM CaCI2 • The use of O.OIM CaCl2
solution for measuring the pH values of soils has the following important
advantages:
(1) The pH of a soil measured in O.OlM CaCl2 is independent of dilu-
tion over a wide range of soil to solution ratios.
(2) The amount of soluble electrolytes contributed by a nons aline soil
60-2 FACTORS AFFECTING SOIL pH 919

in a suspension of 1 part of soil in 2 parts of O.OIM CaCl 2 is insignificantly

small. The observed pH is, therefore, practically independent of the initial
amount of salts present in the soil and thus truly reflects the degree of base
saturation or the lime status of the soil regardless of the time of the year
that the soil sample is taken.
(3) Inasmuch as O.OIM CaCl2 solution is approximately equivalent to
the total electrolyte concentration of the soil solution of a nons aline soil at
optimum field water content, the soil pH measured, e.g., in a suspension of
1 part of soil in 2 parts of O.OIM CaCl2 solution, represents more nearly
the pH of the soil solution under actual field conditions, and, therefore,
should reflect more accurately the H+-ion environment of plant roots and
soil microorganisms than the soil pH measured in a suspension using 1 part
of soil in 2 parts of water.
(4) Because soil suspensions are flocculated in O.OIM CaCl2 , the errors
due to the liquid junction potential can be minimized by placing the calomel
electrode in the clear supernatant liquid.
The pH measured in O.OIM CaCl2 is about 0.5 pH unit lower than that
measured in water using 1 part of soil to 2 parts of liquid, and this should
be borne in mind in interpreting the results of pH measurements made in
O.OIM CaCI2 •
In accordance with the predictions of the Donnan and Gouy theories,
Schofield and Taylor (1955) showed that over a wide range in concentra-
tion of CaCb in the soil suspension, the value of pH - i pCa remained
remarkably constant for any given soil. They introduced the term "lime
potential" for pH - i pCa (actually pH - i p(Ca + Mg» as being char-
acteristic of a given soil and suggested that the results be expressed in terms
of the lime potential by subtracting 1.14, which is the value of i pCa
for O.OIM CaCI2 , from the observed pH value. Inasmuch as the use of the
pH scale has been so firmly established and in view of the possible confusion
of the term "lime potential" with the chemical potential of Ca(OHh, it
seems preferable to report the results of measurements of soil pH in O.OIM
CaCl 2 simply as "pH in O.OIM CaCl2 solution." The relation between
pH - f pCa (lime potential) and the activity of Ca(OHh is given by

pH - ! pCa = t log ctCa(OH12 + 14.2. [7]

60-2.3 Effect of Equilibration of Soils With CO2 of the Air

The effect of CO2 is to decrease soil pH, but this effect of CO 2 at the
partial pressure prevailing in the atmosphere is very small in soils having
pH values below 7. Whitney and Gardner (1943) found that the pH of
calcareous soils is a straight-line function of the logarithm of the CO2
pressure and concluded that the pH of such soils measured after equilibra-
920 HYDROGEN.ION ACTIVITY

tion with known partial pressures of CO 2 should give a better indication of

the probable pH range in the field than the pH measured in water. In the
U. S. Salinity Laboratory (Richards, 1954), the pH measurements are
ordinarily made after equilibration of the soils with the CO2 pressure of the
atmosphere.
It should be obvious from equation [1] in section 59-2.1 that, in cal-
careous soils, the value of pH - i pCa in the soil solution is uniquely fixed
by the CO2 pressure of the air in equilibrium with the soil. At the partial
pressure of CO2 of the air, it can be shown that
pH - ! pCa = 6.60. [8J
Thus the pH of a calcareous soil in equilibrium with the partial pressure
of CO2 of the air should vary with the Ca2 + concentration of the soil solu-
tion in accordance with equation [8] and should thus afford some measure
of the amount of soJuble calcium salts present in the soil. In the presence of
an appreciable amount of exchangeable N a in a calcareous soil in equilib-
rium with the partial pressure of CO2 of the air, the concentration of Ca2 +
in the soil solution will be lower and the pH will be correspondingly higher
than that of pure CaC03 suspension in equilibrium with the partial pressure
of CO2 of the air, but the relationship given by equation [8] should still be
valid.

60-3 SOIL pH BY GLASS ELECTRODE pH METER

60-3.1 Glass Electrode pH Meter

60-3.1.1 VACUUM TUBE VOLTMETER

A vacuum tube voltmeter may be either a potentiometric type, which
is operated as a null-balance meter, or a direct-reading pH meter (Bates,
1954; Willard et aI., 1958). Measurements with the potentiometric type
of pH meter are independent of the vacuum tube circuit characteristics, and
the accuracy of the results depends only on the linearity of the slidewire.
Both types of pH meters are, however, capable of giving satisfactory results
provided that the meter is standardized with two reference buffer solutions
differing in pH by about 2 or 3 pH units.

60-3.1.2 GLASS ELECTRODE

The glass electrode (Dole, 1941; Bates, 1954) consists of a glass mem-
brane of appropriate composition blown into a small bulb which is sealed
to a stem of Pyrex glass. An internal reference electrode, consisting of either
a silver-silver chloride electrode or a calomel electrode, dips into a dilute
solution of HCl placed inside the bulb. The potential of such an electrode
Eg is given by the familiar Nernst equation,
60-3 SOIL pH BY GLASS ELECTRODE 921

RT
ED = Eo +F In aH+
in which the symbols R, T, and F represent the gas constant, the absolute
temperature, and the faraday, respectively, and Eo is a constant which is
determined by the potential of the internal electrode and the pH of the
solution within the bulb of the glass electrode.
Many glass compositions are now used in the fabrication of glass elec-
trodes. The soda-lime glass, Corning 015, which was once in common use,
behaves according to the Nernst equation only between pH 1 and 8. In
extremely acid solutions, the decreased water activity leads to a decrease
in the positive potential of the electrode and causes positive deviations from
the true pH. On the other hand, in extremely alkaline solutions, the alkali
metal ions, especially N a +, enter the glass membrane and give rise to a
more positive potential, which causes negative deviations from the true pH.
In measuring pH values of alkaline solutions containing Na+, proper cor-
rections must be applied from nomographs supplied by the manufacturer.
Special lithium glasses, however, have been developed for use in alkaline
solutions having pH values as high as 13 with only very small errors due to
Na +. Special glass electrodes are also available for pH measurements at
high temperatures.

60-3.J.3 REfERENCE ELECTRODE

A saturated calomel electrode, which is a mercury-mercurous chloride
electrode, is most commonly used as an external reference electrode. Elec-
trical connection with the test solution is usually established through either
a ground-glass joint (sleeve type) or an asbestos fiber projecting through a
small hole in the base of the electrode stem. The sleeve type calomel
electrode is preferred to the asbestos fiber type because it is less subject to
clogging and gives a more reproducible junction potentiaI.

60-3.2 Standard Buffer Solutions

Certified samples of buffer substances, from which NBS standard buffer

solutions (Bates, 1954) listed below can be prepared, may be obtained
from the National Bureau of Standards, U. S. Department of Commerce,
Washington 25, D. C.
1. Potassium biphthalate, 0.05M: Dry KH phthalate for 2 hours at 110°C.
Dissolve 10.21 g. of KH phthalate in distilled water, and dilute the solu-
tion to 1 liter with distilled water. As a preservative, add 1.0 ml. of
chloroform or a crystal (about 10 mm. in diameter) of thymol per liter
of the buffer solution. This solution has a pH value of 4.00 at tempera-
tures from 15° to 30°C.
922 HYDROGEN-ION ACTIVITY

2. Phosphate buffer, 0.025M KH:!P0 4 and 0.025M Na2HP04: Dry the two
phosphate salts, KH 2P0 4 and Na2HP04, for 2 hours at 110°C. Dissolve
3.44 g. of KH 2P04 and 3.55 g. of Na2HP04 in distilled water, and di-
lute the solution to 1 liter with distilled water. As a preservative, add 1.0
ml. of chloroform or a crystal (about 10 mm. in diameter) or thymol
per liter of the buffer solution. This buffer solution has pH 6.90 at 15°C.,
pH 6.88 at 20°C., pH 6.86 at 25°C., and pH 6.85 at 30°C.

60-3.3 Standardization and Care of Glass Eledrode pH Meter

After zeroing the instrument (balancing the amplifier and the potentio-
metric circuit) in accordance with the directions supplied by the manufac-
turer, standardize the meter by immersing the glass and calomel electrodes
into a standard buffer solution and setting the slidewire scale or the indica-
tor needle to the pH of the buffer. This operation corrects for the asymmetry
potential of the glass electrode which may change slightly from day to day.
Rinse the electrodes thoroughly with distilled water, and check the instru-
ment with a second buffer solution differing in pH from the first buffer solu-
tion by 2 or 3 pH units. In subsequent measurements of pH of soils or test
solutions, use one of these standard buffer solutions to check the per-
formance of the pH meter periodically, say after each 5th or 10th measure-
ment.
Clean the glass electrode periodically, if necessary, by soaking it in a
solution of a mild detergent and wiping it with a piece of tissue paper to
remove the film of soil that adheres to the electrode surface. A film of
CaCOa that sometimes forms on the surface of the glass electrode during
measurement of pH of calcareous soils may be removed by dipping the
electrode for a few seconds in dilute HCl and rinsing it with water.
At the beginning of a series of measurements and before standardization
of the pH meter, loosen the sleeve of the calomel electrode to flush the
ground-glass joint with fresh saturated KCl solution. Then reseat the sleeve
firmly, and rinse it with distilled water. To refill the calomel electrode, use
a solution saturated with KCl and calomel (mercurous chloride).
When not in use, keep the glass electrode and the calomel electrode im-
mersed in distilled water.

60-3.4 Method for Soil pH in Water

To 20 g. of soil in a 50-ml. beaker, add 20 ml. of distilled water, and stir

the suspension several times during the next 30 minutes. Let the soil suspen-
60-3 SOIL pH BY GLASS ELECTRODE 923

sion stand for about 1 hour to allow most of the suspended clay to settle out
from the suspension. Adjust the position of the electrodes in the clamps
of the electrode holder so that, upon lowering the electrodes into the beaker,
the glass electrode will be immersed well into the partly settled suspension,
and the calomel electrode will be immersed just deep enough into the clear
supernatant solution to establish a good electrical contact through the
ground-glass joint or the fiber-capillary hole. Then insert the electrodes into
the partly settled suspension as indicated above, measure the pH, and re-
port the results as "soil pH measured in water."

60-3.5 Method for Soil pH in O.OlM CaCI 2 Solution

60-3.5.1 REAGENTS
1. Stock calcium chloride solution (CaCI!!) 3.6M: Dissolve 1,059 g. of
CaCI!!·2H!!O in distilled water in a 2-liter volumetric flask. Cool the
solution, dilute it to volume with distilled water, and mix it well. Dilute
20 ml. of this solution to 1 liter with distilled water in a volumetric flask,
and standardize it by titrating a 25 ml. aliquot of the diluted solution
with standard O.IN AgN0 3 , using 1 ml. of 5% K2Cr04 as the indicator.
2. Calcium chloride (CaCI!!) O.OIM: Dilute 50 ml. of stock 3.6M CaCI!! to
18 liters with distilled water. If the pH of this solution is not between 5
and 6.5, adjust the pH by addition of a little Ca(OHh or HC!. As a
check on the preparation of this solution, measure its electrical conduc-
tivity. The specific conductivity should be 2.32 ± 0.08 mmho. per cm.
at 25°C.

60-3.5.2 PROCEDURE
To 10 g. of soil in a 50-m!. beaker, add 20 ml. of O.OIM CaCl2 solution,
and stir the suspension several times during the next 30 minutes. Let the soil
suspension stand for about 30 minutes to allow most of the suspended clay
to settle out from the suspension. Adjust the position of the electrodes in
the clamps of the electrode holder so that, upon lowering the electrodes into
the beaker, the glass electrode will be immersed well into the partly settled
suspension and the calomel electrode will be immersed just deep enough into
the clear supernatant solution to establish a good electrical contact through
the ground-glass joint or the fiber-capillary hole. Then insert the electrodes
into the partly settled suspension as indicated above, measure the pH, and
report the results as "soil pH measured in O.OIM CaCI 2 ."
924 HYDROGEN·ION ACTIVITY

60-4 SOIL pH BY INDICATORS

60-4.1 Special Apparatus

1. Porcelain test plate: White porcelain test plates, especially made for
this purpose, are commercially available, e.g. La Motte "Morgan" test
kit, manufactured by La Motte Chemical Products Co., Towson, Balti-
more 4, Md. These porcelain plates are usually provided with two com-
partments that are connected by a channel. The soil is treated with an
indicator solution in the upper compartment. After percolating through
the soil, the indicator solution is allowed to drain down the channel into
the lower compartment, where the color of the indicator is compared
with that on the standard color chart of the appropriate indicator.

60-4.2 Indicators

1. Bromocresol green: Triturate 0.4 g. of bromocresol green in an agate

mortar with 6 mI. of 0.1N NaOH until the indicator is dissolved. Dilute
the solution with water to 1 liter, and adjust the pH to 4.8 with 0.1N
NaOH or 0.1N HCl. Preserve the indicator by adding 1 ml. of chloro-
form. The pH interval of this indicator is 3.8 to 5.4.
2. Chlorophenol red: Triturate 0.4 g. of chlorophenol red in an agate mor-
tar with 10 ml. of 0.1N NaOH until the indicator is dissolved. Dilute the
solution with water to 1 liter, and adjust the pH to 6.0 with 0.1N
NaOH or 0.1N HCl. Preserve the indicator solution by adding 1 ml.
of chloroform. The pH interval of this indicator is 4.8 to 6.4.
3. Bromothymol blue: Triturate 0.4 g. of bromothymol blue in an agate
mortar with 7 ml. of 0.1N NaOH until the indicator is dissolved. Dilute
the solution with water to 1 liter, and adjust the pH to 7.0 with 0.1N
NaOH or 0.1N HCl. Preserve the indicator solution by adding 1 ml. of
chloroform. The pH interval of this indicator is 6.0 to 7.6.

60-4.3 Procedure

Place a small representative sample of soil in the upper compartment of

the porcelain test plate and treat the soil with a slight excess of the indi-
cator solution. After about 1 minute, tilt the test plate; and, by means of a
glass rod or a small spatula, draw some of the indicator solution that has
percolated through the soil down the channel into the lower compartment.
Compare the color of this indicator solution with that given on the color
chart of the corresponding indicator. If the soil pH should fall near the end
60-5 LITERATURE 925

of the color range of the indicator, repeat the test using another indicator
that has an overlapping pH range.

60-4.4 Comments

For field use, simplified soil test kits such as the one described above are
commonly used (Jackson, 1958). The results obtained by soil test kits may
deviate as much as 0.3 pH from those given by the electrometric method
(Mason and Obenshain, 1938) owing to turbidity of the indicator solution,
after it has percolated through the soil, and to adsorption of the indicator
by the soil. Even the sulfonphthalein indicators, described in section 60-4.2,
are adsorbed to some extent by soils high in organic matter content (Naftel
ct aI., 1933). Indicators, such as methyl red, that contain basic groups are
adsorbed completely by soils and obviously cannot be used in this method.

60-5 LITERATURE CITED

Bates, R. G. 1954. Electrometric pH Determinations. John Wiley & Sons, Inc., New
York.
Baver, L. D. 1927. Factors affecting the H+-ion concentration of soils. Soil Sci.
23:399-414.
Carolus, R. L., and Lucas, R. E. 1943. Some factors influencing fluctuations in
acidity during period of extreme change in the moisture content of soils. Am. Soc.
Hort. Sci. Proc. 42:507-510.
Chapman, H. D., Oxley, J. H., and Curtis, J. H. 1941. The determination of pH at
soil moisture contents approximating field conditions. Soil Sci. Soc. Am. Proc.
(1940) 5: 191-200.
Clark, W. M. 1923. The Determination of Hydrogen Ions. Ed. 3. Williams and
Wilkins Co., Baltimore.
Coleman, N. T., Williams, D. E., Nielsen, T. R., and Jenny, H. 1951. On the validity
of interpretations of potentiometrically measured soil pH. Soil Sci. Soc. Am. Proc.
(1950) 15: 106-110.
Davis, L. E. 1943. Measurements of pH with the glass electrode as affected by soil
moisture. Soil Sci. 56:405-422.
Dole, M. 1941. The Glass Electrode. John Wiley & Sons, Inc., New York.
Hissink, D. J. 1930. Report of the Committee on Soil Reaction Measurements of the
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