J. Biol. Chem.-1929-Sendroy-197-246 PDF

THE ACTIVITY COEFFICIENTS OF CERTAIN ACID-BASE
INDICATORS.*
BY JULIUS SENDROY, JR., AND A. BAIRD HASTINGS.
(From the Hospital of The Rockefeller Institute for Medical Research,
New York.)
(Received for publication, December 29, 1928.)
At an early stage in the development of the calorimetric method,

Ktister (I), Van Cleeff (2), Acree (3), von Szyszkowski (4), and
Michaelis and Rona (5) recognized and pointed out the fact that
the salt content of the solution influenced the reaction of the indi-
Downloaded from http://www.jbc.org/ by guest on April 15, 2019

cator. The color of the same indicator in the same buffer solution
could be changed by addition of neutral salts. Sorensen and
Palitzsch (6) called attention to the fact that it was necessary to
consider separately, the “neutral salt effect” on the buffer itself,
and on the indicator color. In 1914, Bjerrum (7) suggested that
this double effect had to do with the change in the dissociation
constant of the buffer, and also of the indicator. He found that
the change in the logarithm of the indicator dissociation constant
was proportional to the variation in salt concentration.
The literature covering the work done on “salt errors” of indi-
cators will be found in the texts and monographs of Thiel (S),
Bjerrum (7), Prideaux (9), Michaelis (lo), Kolthoff (ll), and
Clark (12), and will be referred to in connection with the develop-
ment of the text of this paper. Kolthoff, in 1926, summarized
the results in saying that, ‘Various theories have been advanced
to explain the salt error, but none of them is adequate for the
quantitative interpretation of the behavior of every indicator.”
The indicator error caused by different salts has been found to
vary in an apparently irrational manner. The question has
therefore been allowed to rest as a purely empirical matter. ‘Salt
error” has been correlated with percentage salt, equivalent con-
centration, molecular concentration, and sodium ion concentra-
tion. The effect of salt has been determined in most cases at such
* A preliminary report of this work appeared under the above title in the
Proceedings of the American Society of Biological Chemists, J. Biol. Chem.,
78, p. lxvii (1928).
197
198 Indicator Activity Coefficients
high concentrations of electrolyte as to be of little help in biological
work, where solutions are seldom used of an electrolyte strength
exceeding that of 0.9 per cent NaCl.
It is important to note, however, that in 1921, Brijnsted (13),
on the basis of some of Sorensen’s old data, suggested that the
behavior of some indicators, including phenolphthalein and neutral
red, might be due to the effect of interionic forces in electrolytic
solutions. He obtained good agreement between Sorensen’s data
and the theoretical equations which he and Bjerrum had devel-
oped on the basis of the former’s theory of complete dissociation.
In the present paper we have attempted to utilize recent ad-

vances in the theory of solutions to study indicator behavior in the
presence of salts. The indicators studied have been brom-cresol
green, brom-cresol purple, and phenol red, covering the pH range
from 4.0 to 8.2. A theory, originally suggested by BrBnsted, has
been further developed and applied to the systematic quantitative
investigation of the change in color of these indicators under the
influence of certain salts.
THEORETICAL.
The theoretical aspects of indicator color change are sufficiently

discussed in the texts referred to above, so that it will be neces-
sary to present here only a brief outline of the situation.
The indicators which we have studied may be structurally
represented in two dimensional space as follows :
Phenol red. Brom-cresol purple. Brom-cresol green.
Mol. wt. = 354 Mol. wt. = 540 Mol. wt. = 698
f) ,,,,f) Ci&()Br Br~CX~ zaQBr Bg Y,,
\ \/ \/
C-O c-o c-o
’ I/;’ ’ I//O ’ j//O

-s -S --s
\
0 0 0 \O 0 \O
Phenolsulfon- Dibromo-o-cresol Tetrabromo-m-cresol
phthalein. sulfonphthalein. sulfonphthalein.
J. Sendroy, Jr., and A. B. Hastings 199
The exact configuration of these compounds with respect to the
bromine positions is not known.
According to the original theory of Wilhelm Ostwald, indicators
are weak acids or weak bases, in which the color of the undisso-
ciated form is different from that in the dissociated or ionized form.
There have been some objections to this idea, among them (1) the
alkali salts of phenol red are red in the solid form as well as in
solution, (2) some indicator color changes show a definite time
reaction (they are either ionic reactions of a higher order or more
likely not ionic, but molecular reactions), and (3) Beer’s law is
obeyed in solutions of solvents other than water.

On the other hand, the school of Hantzsch and his collaborators
has evolved the tautomeric or chromophoric theory, according
to which the color of an indicator is a function of its constitution;
that is, it depends on the equilibrium between a la&one form (such
as colorless phenolphthalein in acid solution) and a quinone (such
as red phenolphthalein in alkaline solution). However, as Kol-
thoff states, the structural change may be a phenomenon parallel
to the color change, and yet not really be the cause of it. Also,
the correlation between color and pH is not explained according
to this theory without some assumption of ionization.
One may combine the two theories as Stieglitz (14) and Kolthoff
have proposed. Thus, there is not only an equilibrium between
the lactone and quinone forms [LtiQ], but the quinone form will
also be in equilibrium with Q- ions and Hf ions [Q+Q- + Hf].
The ions may or may not have the same constitutions as the
undissociated molecules, and the final equilibrium constant
evolved, although an “apparent” equilibrium constant, yields an
expression which agrees with the simple Wilhelm Ostwald form of
equation. For example, brom-cresol green will behave in this
manner :
‘c’-0
’ I//O
-S
0 \O
Colorless lactone Colored acid quinone
(weak acid). cresolate (strong acid).
0- + K+ ;;
Br Br Br Br
CH, CH,
0 0
‘11
C
1 i
0 -S-O- + K+
II
0
Colored salt

(strong acid).
The sulfonphthaleins are dibasic acids. However, the dissocia-

tion constant of the sulfonic acid group is so much stronger than
that of the weak phenolic group with which the color change is
mainly associated, that they may be and have been regarded as
monobasic for most purposes.
In the following treatment, we may most simply consider the
indicator as a weak acid, the salt or alkaline form, BA, of which is
completely ionized, the acid, HA, not ionized to any significant
extent. Consequently, all of the A- anions will be derived from,
and equal in concentration to BA. If the activity coefficient of
the undissociated acid is assumed to be unity,
(1) K’ = R
TA-
where K’ denotes the apparent stoichiometric dissociation con-

stant, K the apparent activity dissociation constant (the value
of K’ at infinite dilution), and YA- the activity coefficient of the
anion. If p is used to denote negative logarithm, the expression
showing the relation between the hydrogen ion activity and the
two forms of the indicator will then be the familiar Henderson-
Hasselbalch equation:
DA1
(2) p@H+ = PK’ + log [HA]
Also, from Equation 1,

(3) pK’ = pK - pTA- = pK - ApK’
and for a dibasic acid,

(4) pKz’ = p& + p’yA- - p’yA- = PIG - ApIG’
The ratio [BA] : [HA] may be altered by change of either

paH+ Or Of pK’. In other words, with change in pK’ there is the
possibility of an alteration in color of a solution with pan+ un-
changed. When Equation 1 is applied to an indicator, BA is
calculated as the colored alkali salt. In this case the pK’ indi-
cates both ionic and tautomeric equilibria. Since a constant
fraction of BA is presumably tautomerized into the colored
form of the indicator under any given set of conditions, this
constancy may be incorporated into the general equilibrium

constant K’.
That the Debye-Htickel equation makes possible an approximate
quantitative calculation of the effect of neutral salts on the ap-
parent dissociation constants of weak acids has been shown in a
number of instances. Working with pure buffer solutions,
Hastings and Sendroy (15) applied the Debye-Htickel theory
to the study of the first and second dissociation constants of car-
bonic acid. Since then Cohn has studied the second dissociation
constant of phosphoric acid (16) and more recently the dissociation
constant of acetic acid (17). Simms (18) has recently applied the
theory to the investigation of systems of weak electrolytes of
organic nature.
The Debye-Hiickel theory of interionic activity (19) is ex-
pressed in terms of activity coefficients, and involves the assump-
tion of complete dissociation. When the ions are assumed to
function as point charges, the Debye-Hiickel equations reduce to
the limiting law of Bronsted and La Mer (20).
For a single ion,
(5) - log yion = 0.5 v2 &Y
where y is the activity coefficient, v is the valence of the ion, and

p denotes the ionic strength, a unit of concentration introduced
by Lewis and Randall (21). Since p = + cv2, where c = molar or
molal concentration, a molar solution of NaCl and one of MgS04
of the same strength will be as 1: 1 in molar concentration, but as
1: 4 in ionic strength. Where two ions are involved,
(6) log y’ = 0.5 (v*2 - v12) 4

YZ
or for monovalent and divalent ions,
(7)
However, at higher concentrations, the ions must be regarded as

finite spheres of rigid size and the Debye-Hiickel equation is:
A. v= d/.~
(8) log Yion = XCP
1+04
where A is a universal constant based on the absolute tempera-
ture, the dielectric constant of water, and the Boltzmann distri-

bution coefficient; B is the composite constant involving the effec-
tive thickness of the ionic atmosphere (about 0.33 X lo8 4; cm.)
and the size of the ions (usually about 2 to 5 X 10V8 cm.). C is a
“salting out” term or polarization or hydration term for higher
concentrations, to take account of the effect of change in dielectric
constant of the environment of the particular ions whose activity
is being studied. In our work, this last term can probably be
neglected without causing any appreciable error, the concentra-
tions here being no higher than P = 0.2.*
EXPERIMENTAL.
Procedure and Methods.

In order to obtain reproducible and constant potentials with the
hydrogen electrode, it was necessary to buffer the solutions studied.
Accordingly, phosphate and acetate mixtures of definite com-
position were prepared, diluted to the lowest concentrations
indicated in the tables of results (M/210 acetates, and M/150 phos-
phates), and varying amounts of salt solutions of acetates, phos-
phates, NaC1, KCl, Na2S04, K804, CaCL, MgCL, and MgSOd
were added to increase the ionic strength to about ,u = 0.2. The
composition of all stock solutions was checked quantitatively
* It is recognized that differences in the physical and chemical constitu-
tion of solutions may cause differences in light absorption, quite apart from
the effect of these differences on the ratio of the two forms of indicator as
influenced by the reaction of the solution and the apparent dissociation
constant of the indicator. The work of van Halban and Ebert (22), however,
would seem to indicate that these effects at our concentrations of indicator
and salt would be very slight, and probably negligible.
by standard methods. To study the effect, if there is any, of a
non-electrolyte, some experiments were carried out in which a
glucose solution was used as diluent. In order to have the con-
centrations of solutions the same for both electrometric and
calorimetric observations, they were diluted -& (9cc. + 1 cc. water)
for the electrometric determinations, since the indicator addition
produced the same result of dilution for the calorimetric method.
The water used for all work was freshly redistilled from acid
dichromate. All observations were made at 20 &O.l”, colori-
metric determinations being made in duplicate, electrometric until
three consecutive determinations showed no greater variation than
0.2 miIlivolt.

In order to avoid difficulty due to the presence of minute
amounts of O2 in these dilute solutions, the extra precaution was
taken of bubbling hydrogen gas through them before making the
electrometric observations. The hydrogen electrode apparatus
has already been described (23). The standard solution used to
obtain e, the value of the saturated calomel half-cell, was 0.1
N HCI, made from Hulett’s constant boiling acid. The pan+
was assumed to be 1.08. New platinum-coated electrodes were
used for each experiment, the e being determined before and fre-
quently after all determinations were made.
For connecting bridge, saturated KC1 solution was employed.
Our calculations involve the assumption that the liquid junction
potential between the solution under investigation and the satu-
rated KC1 was the same in all of the solutions studied, including the
0.1 N HCl used for standardization. When we consider the differ-
ent ions and ionic strengths involved in these studies, it may be
questionable whether such an assumption of zero diffusion poten-
tial in each case is justified. However, the error from this source
is apparently but slight in the use of the saturated KC1 bridge.
The calorimetric determinations were made by adding 1 cc. of
indicator (0.016 per cent brom-cresol green, 0.016 to 0.032 per
cent brom-cresol purple, or 0.0075 per cent phenol red) to 9 cc.
of the solution, and reading by daylight lamp against bicolor
standards, as described in previous papers (24,25). These stand-
ards depend only on the relative amounts (measured and known),
of indicator in full acid and full alkaline form. Complicating
factors, such as the fading of the standards, the assumption of a
pK’ value for the indicator, or the consideration of the ionic
strength of the standards, as in the case of phosphate andacetate
buffer standards, were thereby eliminated. The concentration of
indicator made according to Clark, with 1 equivalent of alkali,
was only 0.00002 to 0.00006 M, not sufficient to contribute to or
affect the buffering power of the solution, or its ionic strength.*
0 0.02 006 008 01 0.14
Ho25 salt per Liter

FIG. 1. Electrometric and calorimetric determinations of buffers at
various dilutions.
1 Acknowledgment should be made to the La Motte Chemical Company

and to Hynson, Westcott and Dunning for supplying us with pure indi-
cators for these experiments. No further purification was attempted by us.
Several successive samples of these indicators gave identical titration
curves in accordance with theory as shown by us previously (25). The
titration curve of each indicator was theoretical for a solution containing a
single weak acid. If other phenolphthalein derivatives had been present
in significant proportions they would have measurably distorted the titra-
TABLE I.
Brom-Cresol Green pK’ Change at 20” with Increase of Ionic Strength by Means
of Sodium Acetate. Calorimetric Readings with Indi-
cator Concentration = O.OOOO!J M.
Electro- Colori-
Composition. metric
Sai?o?e HCrHaOz NaGHa
P G
metric
paH+’ olor ratk
log R.
,: I
pK’ in-
dicator. A pK’
_______- --
I pyokg. M p&kg.
2 2
1 0.00130 0.00303 0.00303 0.055 5.08 0.21 4.87 0.05

la 0.00130 0.00303 0.00303 0.055 5.08 0.23 4.85 0.07
2 0.00260 0.00606 0.00606 0.078 5.06 0.24 4.82 0.10

2a 0.00260 0.00606 0.00606 0.078 5.08 0.24 4.84 0.08
3 0.00390 0.00909 0.00909 0.095 5.05 0.25 4.80 0.12

3a s.00390 0.00909 0.00909 0.095 5.06 0.25 4.81 0.11
4 0.00650 0.01515 0.01515 0.123 5.04 0.26 4.78 0.14

4a 0.00650 0.01515 0.01515 0.123 5.06 0.26 4.80 0.12
5 0.01040 0.02424 0.02424 0.156 5.03 0.27 4.76 0.16

5a 0.01040 0.02424 0.02424 0.156 5.04 0.26 4.78 0.14
6 0.01427 0.03333 0.03333 0.182 5.03 0.27 4.76 0.16

6a 0.01427 0.03333 0.03333 0.182 5.03 0.27 4.76 0.16
7 0.01948 0.04545 0.04545 0.213 5.01 0.28 4.73 0.19

7a 0.01948 0.04545 0.04545 0.213 5.02 0.29 4.73 0.19
8 0.02468 0.05757 0.05757 0.240 5.01 0.29 4.72 0.20

8a 0.02468 0.05757 0.05757 0.240 5.02 0.30 4.72 0.20
9 0.03117 0.07272 0.07272 0.270 5.01 0 30 4.71 0.21

9a 0.03117 0.07272 0.07272 0.270 5.02 0.31 4.71 0.21
10 0.03896 0.09093 0.09090 0.301 5.01 0.31 4.70 0.22

10 a 0.03896 0.03090 0.09090 0.301 5.01 0.32 4.69 0.23
-
tion curves, except in the improbable case that the impurity had the same
pK’ as the pure indicator. The nature of our reproducible results indicates
that we were dealing with substances of a considerable degree of purity.
In the case of brom-cresol green many early preparations were unusable
owing to the presence of an insoluble impurity. With later preparations
we had no such difficulty. These melted sharply at 215.5” (Cohen reports
217”; Cohen, B., Pub. Health Rep., U. S. P. H. S., 41,305l (1926)) andgave
reproducible titration curves. Brom-cresol purple melted at 243”. The
phenol red had no definite melting point; it decomposed at about 240”.
TABLE II.
Brom-Cresol Green pK’ Change at 20” with Increase of Ionic Strength by
Means of Sodium Chloride. Calorimetric Readings
with Indicator Concentration = 0.0000% M.
-
Composi- C&Xi-
ion: acetate Electro-
Sample metric metric PK’
NO. 8 in Samph
2, Table I,
P v5- paH+.
hr ratio: ndicator. ApK
+ NaCI. log R.
--
M per kg.
Hz0
I 0.00000 0.00606 0.078 5.07 0.24 4.83 0.09
la 0.00000 0.00606 0.078 5.07 0.24 4.83 0.09

2 0.00909 0.01515 0.123 5.04 0.25 4.79 0.13
2a 0.00909 0.01515 0.123 5.06 0.25 4.81 0.11
3 0.01818 0.02424 0.156 5.03 0.26 4.77 0.15

3a 0.01818 0.02424 0.156 5.03 0.26 4.77 0.15
4 0.02727 0.03333 0.182 5.01 0.27 4.74 0.18

4a 0.02727 0.03333 0.182 5.01 0.27 4.74 0.18
5 0.04545 0.05151 0.227 5.00 0.28 4.72 0.20

5a 0.04545 0.05151 0.227 5.00 0.28 4.72 0.20
6 0.06363 0.06969 0.264 4.98 0.30 4.68 0.24

6a 0.06363 0.06969 0.264 4.99 0.30 4.69 0.23
7 0.08181 0.08787 0.296 4.97 0.31 4.66 0.26

7a 0.08181 0.08787 0.296 4.97 0.31 4.66 0.26
8 0.10908 0.11514 0.339 4.96 0.32 4.64 0.28

8a 0.10908 0.11514 0.339 4.97 0.33 4.64 0.28
9 0.13635 0.14241 0.377 4.94 0.33 4.61 0.31

9a 0.13635 0.14241 0.377 4.96 0.34 4.62 0.30
10 0.16362 0.16968 0.412 4.93 0.34 4.59 0.33

10 a 0.16362 0.16968 0.412 4.95 0.35 4.60 0.32
0.21210 0.21816 0.467 4.93 0.36 4.57 0.35

-
RESULTS.
When a ~/15 phosphate solution of about pq+ = 7.4, such as is

used for color standards, is diluted in several steps to 30 times its
TABLE III.
Means of Potassium Chloride. Calorimetric Readings
with Indicator Concentration = 0.00002 M.
- - -.
hnposi- Colori-
Sample
t :n: acetate Electro-
metric metric PK’
in &mph P hr ratio: dicator.
A pK’
No.
, Table I, paH+’
log R.
+ KCl.
_- _- _- --
Y pHergkg.
2
1 0.00000 3.00606 0.078 5.07 0.22 4.85 0.07
1% 0.00000 3.00606 0.078 5.09 0.24 4.85 0.07
lb 0.00000 3.00606 0.078 5.07 0.24 4.83 0.09

2 0.00909 0.01515 0.123 5.06 0.24 4.82 0.10
2a 0.00909 0.01515 0.123 5.04 0.25 4.79 0.13
3 0.01818 0.02424 0.156 5.04 0.27 4.77 0.15

3a 0.01818 0.02424 0.156 5.03 0.26 4.77 0.15
4 0.02727 0.03333 0.182 5.03 0.29 4.74 0.18

4a 0.03030 0.03636 0.191 5.02 0.29 4.73 0.19
5 0.04545 0.05151 0.227 5.02 0.30 4.72 0.20

5a 0.04545 0.05151 0.227 5.01 0.31 4.70 0.22
6 0.06363 0.06969 0.264 5.01 0.31 4.70 0.22

6a 0.06363 0.06969 0.264 4.99 0.32 4.67 0.25
6b 0.06363 0.06969 0.264 5.00 0.32 4.68 0.24
7 0.08181 0.08787 0.296 5.00 0.34 4.66 0.26

7a 0.08181 0.08787 0.296 5.00 0.34 4.66 0.26
8 0.10908 0.11514 0.339 4.99 0.34 4.65 0.27

8a 0.10908 0.11514 0.339 4.99 0.35 4.64 0.28
8b 0.10908 0.11514 0.339 4.98 0.35 4.63 0.29
9 0.13635 0.14241 0.377 4.98 0.35 4.63 0.29

9a 0.13635 0.14241 0.377 4.98 0.35 4.63 0.29
9b 0.13635 0.14241 0.377 4.98 0.36 4.62 0.30
10 0.16362 0.16968 0.412 4.98 0.35 4.63 0.29

10 a 0.16362 0.16968 0.412 4.97 0.36 4.61 0.31
10 b 0.16362 0.16968 0.412 4.98 0.36 4.62 0.30
11 0.19998 0.20604 0.460 4.97 0.36 4.61 0.31

11 a 0.19998 0.20604 0.460 4.97 0.36 4.61 0.31
11 h 0.19998 0.20604 0.460 4.96 0.37 4.59 0.33
TABLE IV.
Brom-Cresol Green pK’ Change at’ 20” with Increase of Ionic Strength by
Means of Sodium Sulfate. Calorimetric Readings with
Indicator Concentration = 0.00002 M.
Chmposi- COlOri-
ion: acetate Electro-
metric
SaNmoq1e 9 in Sampb
2, Table I,
P
metric
paH+
:olor ratio:
1ogR.
PK
odicator. A pK’
+ NazS0~
M rergkg.
2
1 0.00000 0.00606 0.078 5.06 0.24 4.82 0.10
la 0.00000 0.00606 0.078 5.09 0.24 4.85 0.07

2 0.00303 0.01515 0.123 5.06 0.25 4.81 0.11
2a 0.00303 0.01515 0.123 5.06 0.25 4.81 0.11
3 0.00606 0.02424 0.156 5.05 0.26 4.79 0.13

3a 0.00606 0.02424 0.156 5.03 0.26 4.77 0.15
4 0.00909 0.03333 0.182 5.04 0.27 4.77 0.15

4a 0.00909 0.03333 0.182 5.03 0.27 4.76 0.16
5 0.01515 0.05151 0.227 5.01 0.28 4.73 0.19

5a 0.01515 0.05151 0.227 5.03 0.29 4.74 0.18
6 0.02424 0.06969 0.264 5.01 0.30 4.71 0.21

6a 0.02424 0.06969 0.264 5.00 0.30 4.70 0.22
7 0.02727 0.08787 0.296 5.00 0.31 4.69 0.23

7a 0.02727 0.08787 0.296 4.99 0.31 4.68 0.24
8 0.03636 0.11514 0.339 4.99 0.32 4.67 0.25

8a 0.03636 0.11514 0.339 4.99 0.32 4.67 0.25
9 0.04545 0.14241 0.377 4.98 0.33 4.65 0.27

9a 0.04545 0.14241 0.377 4.98 0.33 4.65 0.27
10 0.05454 0.16968 0.412 4.98 0.34 4.64 0.28

10 a 0.05454 0.16968 0.412 4.97 0.34 4.63 0.29
11 0.06666 0.20604 0.454 4.95 0.35 4.60 0.32

11 a 0.07070 0.21816 0.467 4.96 0.35 4.61 0.31
12 0.08060 0.24786 0.498 4.94 0.36 4.58 0.34

TABLE V.
BTOm-CTeSOl Green pK’ Change at 20” with Increase of Ionic Strength by
Means of Potassium Sulfate. Calorimetric Readings with
Indicator Concentration= 0.00002M.
- - - -
hnposi- Cdori-
tit ,n: acetate Electro-
Sax’e a* in Sample
2, Table I,
p.
metric
p”IH+’ 00
metric
lor ratio:
1ogR.
PK’
dioator. A pK’
k K&304.
.- _- _-
dd rergkg.
2
1 0.00000 I.00606 0.078 5.07 0.24 4.83 0.09
la 0.00000 j.00606 0.078 5.07 0.24 4.83 0.09

2 0.00228 I.01288 0.113 5.07 0.25 4.82 0.10
2a 0.00228 I.01288 0.113 5.07 0.25 4.82 0.10
3 0.00455 1.01969 0.140 5.06 0.25 4.81 0.11

3a 0.00455 I.01969 0.140 5.06 0.26 4.80 0.12
4 0.00682 3.02652 0.163 5.05 0.26 4.79 0.13
4a 0.00682 0.02652 0.163 5.05 0.27 4.78 0.14
5 0.01137 0.04015 0.203 5.04 0.27 4.77 0.15
5a 0.01137 0.04015 0.203 5.04 0.28 4.76 0.16
6 0.01591 0.05379 0.232 5.03 0.29 4.74 0.18

6a 0.01591 0.05379 0.232 5.02 0.30 4.72 0.20
7 0.02046 0.06742 0.26C 5.02 0.30 4.72 0.20

7a 0.02046 0.06742 0.26C 5.02 0.31 4.71 0.21
8 0.02727 0.08787 0.29f 5.01 0.32 4.69 0.23

8a 0.02727 0.08787 0.29E 5.00 0.32 4.68 0.24
9 0.03409 0.10833 0.32E 0.34 4.67 0.25

9a 0.03409 0.10833 0.32s 0.33 4.67 0.25
10 0.04091 0.12879 0.35: 0.34 4.66 0.24

10a 0.04091 0.12879 0.35s 0.34 4.66 0.24
11 0.05303 0.16514 0.40( 4.98 0.35 4.63 0.21

- - - -
original volume, and the calorimetric pan+ is read against the

original ~/15 standards at each dilution, with indicator concen-
trations constant, the result obtained with phenol red is such as is
Indicator Activity Coefficients
TABLE VI.
Brom-Cresol Green pK’ Change at 20” with Increaseof Ionic Strength by
Means of Calcium Chloride. Calorimetric Readingswith
Indicator Concentration= 0.00002M.
- -Y-
Composi- Colori-
.ion: acetate Electro-
Sai%-?e ts in Sampl F2 P di- metric metric
:dor ratio
PK’
ndicatotor A pK’
2, Table I, PaH+. log R.
+ CaC12.
-
M per kg.
Hz0
1 0.00000 0.00604 0.078 5.08 0.24 4.84 0.08
la 0.00000 0.00604 0.078 5.09 0.24 4.85 0.07

2 0.00312 0.01540 0.124 5.05 0.25 4.80 0.12
2a 0.00312 0.01540 0.124 5.04 0.26 4.78 0.14
3 0.00624 0.02478 0.157 5.03 0.27 4.76 0.16

3a 0.00624 0.02478 0.157 5.04 0.28 4.76. 0.16
4 0.00937 0.03414 0.185 5.01 0.29 4.72 0.20
4a 0.01025 0.03679 0.192 5.01 0.30 4.71 0.21
5 0.01561 0.05287 0.230 4.99 0.31 4.68 0.24

5a 0.01538 0.05218 0.228 5.01 0.31 4.70 0.22
6 0.02186 0.07160 0.267 4.98 0.33 4.65 0.27

6a 0.02153 0.07063 0.266 4.96 0.32 4.64 0.28
7 0.02810 0.09034 0.300 4.96 0.34 4.62 0.30

7a 0.02769 0.08910 0.298 4.96 0.33 4.63 0.29
8 0.03747 0.11844 0.344 4.95 0.35 4.60 0.32

8a 0.03691 0.11677 0.341 4.93 0.33 4.60 0.32
9 0.04684 0.14654 0.382 4.92 0.35 4.57 0.35

9a 0.04614 0.14445 0.380 4.92 0.34 4.58 0.34
10 0.05620 0.17464 0.417 4.91 0.35 4.56 0.36

10a 0.05536 0.17212 0.415 4.90 0.34 4.56 0.36
11 0.07286 3.22460 0.473 4.88 0.36 4.52 0.40
11a 0.07177 3.22135 0.470 4.89 0.35 4.54 0.38
-
shown in Fig. 1. The apparent slight pffn+ change is in the direc-

tion of an increase with dilution. The same procedure with a
TABLE VII.
Means of Magnesium Chloride. Calorimetric Readings with
Indicator Concentration = 0.00002hf.
- -- - ___
Composi-
tion: aoetat .e Electro- Colori-
a8 in
sal21f Sample 2,
Ta$;.\,+
P
4 metric
PaH+.
metric
oh ratic
log R.
PK’
ndioatm A pK’
-- - ___ __
Y per kg.Hz 0
1 0.00000 0.00604 kO78 5.07 0.24 4.83 0.09
la 0.00000 / 0.00604 0.078 5.07 0.24 4.83 0.09
2 0.00327 0.01585 0.126 5.03 0.26 4.77 0.15

2a 0.00327 0.01585 0.126 5.03 0.26 4.77 0.15
3 0.00655 0.02568 0.160 5.02 0.28 4.74 0.18
3a 0.00655 0.02568 0.160 5.01 0.29 4.72 0.20
4 0.00982 0.03549 0.188 5.00 0.30 4.70 0.22
4a 0.01090I 0.03875 0.197 5.00 0.30 4.70 0.22
5 0.01527 0.05185 0.228 4.97 0.31 4.66 0.26
5a 0.01527 0.05185 0.228 4.97 0.31 4.66 0.26
6 0.02181 0.07147 0.267 4.95 0.32 4.63 0.29

6a 0.02181 0.07147 0.267 4.96 0.32 4.64 0.28
7 0.02836 0.09110 0.302 4.94 0.33 4.61 0.31
7a 0.02836 0.09110 0.302 4.95 0.32 4.63 0.29
8 0.03708 0.11728 0.343 4.92 0.34 4.58 0.34

8a 0.03708 0.11728 0.343 4.93 0.33 4.60 0.32
9 0.04580 0.14345 0.379 4.90 0.34 4.56 0.36
9a 0.04580 0.14345 0.379 4.91 0.34 4.57 0.35
10 0.05672 3.17618 0.420 4.88 0.35 4.53 0.39

10 a 0.05672 3.17618 0.420 4.90 0.34 4.56 0.36
11 0.07198 3.22198 0.471 4.86 0.35 4.51 0.41

11 a 0.07198 3.22198 0.471 4.87 0.35 4.52 0.40
- -
~/15 phosphate mixture of pan+ about 6.4 and brom-cresol purple

yields a similar result. On the other hand, with a ~/7 acetate
mixture of po(n+ about 5.0 and brom-cresol green, the curve ob-
tained indicates, with reference to the original standard, a pQ(n+
decreasing with dilution.
An inspection of the electrometric dilution curves shows that
there is no essential difference in the behavior of the phosphates
and acetates, but that the above outlined difference is due to the
fact that the buffer salts have other, though lesser, effects on the
indicators than the effect exerted through pffn+. In each case,
dilution of the buffer results in an increase of the actual po(n+
determined electrometrically. The calorimetric and electro-
metric observations agree at one point only; namely, at the con-
centration of salt corresponding to that of the calorimetric stand-

TABLE VIII.
Brom-Cresol Green pK’ at SO" with Addition of Glucose. Calorimetric
Readings with Indicator Concentration= 0.00008
M.
Chmposi-
tion: acetate Electro- Colori-
as in metric metric PK’ ApK
Sample 2, B ndicator.
color ratio:
P’=H+. log R.
r$20k.+
_- _-
Afpal.
0.0000 0.00604 0.078 5.07 0.24 4.83 0.09

0.0111 0.00604 0.078 5.08 0.25 4.83 0.09
0.0222 0.00604 0.078 5.07 0.24 4.83 0.09
0.0333 0.00604 0.078 5.07 0.25 4.82 0.10
0.0555 0.00604 0.078 5.07 0.24 4.83 0.09
0.0888 0.00604 0.078 5.06 0.25 4.81 0.11
0.1333 0.00604 0.078 5.07 0.24 4.83 0.09
0.2000 0.00604 0.078 5.05 0.24 4.81 0.11
-
ards used for the color readings. Increased concentration again

causesa divergence of the two curves, but the discrepancy is of a
different sign. Thus the relative salt concentrations of the un-
known material and the color standard determine the magnitude
and the algebraic sign of what is known in the literature as “salt
error.” In the sensein which it is used in this paper, this is the
difference between the calorimetric and the electrometric readings :
P”H+(C) - wH+(e>.
The experimental data and the results obtained are given in
Tables I to XXIII inclusive. The values of pK’ of the indicators
were calculated according to Equation 2 from the electrometric
TABLE IX.
Brom-Cresol Purple pK’ Change at 20” with Increase of Ionic Strength by
Means of Sodium and Potassium Phosphates. Calorimetric
Rea&ngs with Indicator Concentrakon = 0.00005 M.
Colori-
Electro- metric PK'
SaNmople metric OOh indi- A pK’
PaH+. ratio: cator.
log R.
M per M per
kg.H?O kg.WzO
1 0.00144 0.00057 0.00314 0.056 6.69 0.30 6.39 0.07

la 0.00144 0.00057 0.00314 0.056 6.69 0.30 6.39 0.07
2 0.00288 0.00113 0.00628 0.079 6.68 0.29 6.39 0.07

2a 0.00288 0.00113 0.00628 0,079 6.67 0.30 6.37 0.09
3 0.00433 0.00170 0.00943 0.097 6.66 0.29 6.37 0.09

3a 0.00433 0.00170 0.00943 0.097 6.65 0.29 6.36 0.10
4 0.00576 0.00227 0.01256 0.112 6.64 0.28 6.36 0.10

4a 0.00576 0.00227 0.01256 0.112 6.64 0.30 6.34 0.12
5 0.00866 0.00340 0.01886 0.137 6.61 0.28 6.33 0.13

5a 0.00866 0.00340 0.01886 0.137 6.58 0.29 6.29 0.17
6 0.01299 0.00510 0.02829 0.168 6.57 0.27 6.30 0.16

6a 0.01299 0.00510 0.02829 0.168 6.58 0.30 6.28 0.18
7 0.01732 0.00680 0.03772 0.194 6.55 0.27 6.28 0.18

7a 0.01732 0.00680 0.03772 0.194 6.56 0.29 6.27 0.19
8 0.02165 0.00850 0.04716 0.217 6.52 0.27 6.25 0.21

8a 0.02165 0.00850 0.04716 0.217 6.53 0.28 6.25 0.21
9 0.02598 0.01020 0.05658 0.238 6.50 0.26 6.24 0.22

9a 0.02598 0.01020 0.05658 0.238 6.51 0.27 6.24 0.22
10 0.03174 0.01247 0.06913 0.263 6.48 0.26 6.22 0.24

10 a 0.03174 0.01247 0.06913 0.263 6.49 0.26 6.23 0.23
11 0.03754 0.01475 0.07677 0.277 6.46 0.25 6.21 0.25

11 a 0.03754 0.01475 0.07677 0.277 6.46 0.24 6.22 0.24
12 0.04330 0.01700 0.09431 0.307 6.44 0.23 6.21 0.25

12 a 0.04330 0.01700 0.09431 0.307 6.44 0.23 6.21 0.25
TABLE X.
Brom-Cresol Purple pK’ Change at 20” with Increase of Ionic Strength by
Means of Sodium Chloride. Calorimetric Readings with
Composi-
tion:
phosphate Electrc- Colori-
Sam&lye as in metric metric PK’ A pK’
P
Sample 3, PaH+. 0101 ratio: ldioator.
Table IX, log R.
+ N&l.
r per kg.HzC
1 0.00000 0.00948 0.097 6.65 0.28 6.37 0.09
la 0.00000 0.00948 0.097 6.60 0.29 6.31 0.15

2 0.00914 0.01862 0.136 6.59 0.28 6.31 0.15
2a 0.00914 0.01862 0.136 6.58 0.28 6.30 0.16
3 0.01828 0.02776 0.167 6.56 0.28 6.28 0.18

3a 0.01828 0.02776 0.167 6.53 0.28 6.25 0.21
4 0.02742 0.03690 0.192 6.52 0.27 6.25 0.21

4a 0.02742 0.03690 0.192 6.51 0.27 6.24 0.22
5 0.04570 0.05518 0.235 6.48 0.26 6.22 0.24

5a 0.04570 0.05518 0.235 6.46 0.26 6.20 0.26
6 0.06398 0.07346 0.271 6.43 0.24 6.19 0.27

6a 0.06398 0.07346 0.271 6.42 0.24 6.18 0.28
7 0.08226 0.09174 0.303 6.38 0.22 6.16 0.30

7a 0.08226 0.09174 0.303 6.38 0.22 6.16 0.30
8 0.10968 0.11916 0.345 6.34 0.20 6.14 0.32

8a 0.10968 0.11916 0.345 6.35 0.21 6.14 0.32
9 0.13710 0.14658 0.383 6.31 0.18 6.13 0.33

9a 0.13710 0.14658 0.383 6.31 0.19 6.12 0.34
10 0.16452 0.17400 0.417 6.28 0.15 6.13 0.33

10 a 0.16452 0.17400 0.417 6.29 0.17 6.12 0.34
pan+ and the calorimetric readings of the samples against bicolor

standards. The standards were marked in terms of the logarithm
of the ratio of the alkaline to the acid form of the indicator. The
values of pK’ so calculated involve the experimental errors in de-
termination of pan+ electrometrically and calorimetrically, which
TABLE XI.
Brom-Cresol Purple pK’ Change at 20" with Increase of Ionic Strength by
Means of Potassium Chloride. Calorimetric Readings with
Indicator Concentration = 0.00005JX.
Cyyi-
phosphate Electrc- C&Xi-
as in metric metric PK’ A pK’
P G PaH+. 31or ratio: idicator.
log R.
wrkg.HzO
1 0.00000 0.00948 0.097 6.64 0.28 6.36 0.10
1% 0.00000 0.00948 0.097 6.65 0.29 6.36 0.10

2 0.00910 0.01858 0.136 6.58 0.27 6.31 0.15
2a 0.00910 0.01858 0.136 6.59 0.28 6.31 0.15
3 0.01820 0.02768 0.166 6.56 0.27 6.29 0.17

3a 0.01820 0.02768 0.166 6.56 0.28 6.28 0.18
4 0.02730 0.03678 0.192 6.52 0.27 6.25 0.21

4a 0.02730 0.03678 0.192 6.53 0.27 6.26 0.20
5 0.04550 0.05498 0.234 6.49 0.26 6.23 0.23

5a 0.04550 0.05498 0.234 6.48 0.26 6.22 0.24
6 0.06370 0.07318 0.270 6.44 0.24 6.20 0.26

6a 0.06370 0.07318 0.270 6.44 0.25 6.19 0.27
7 0.08190 0.09138 0.302 6.42 0.23 6.19 0.27

7a 0.08190 0.09138 0.302 6.42 0.24 6.18 0.28
8 0.10920 0.11868 0.344 6.37 0.21 6.16 0.30

8a 0.10920 0.11868 0.344 6.38 0.23 6.15 0.31
9 0.13650 0.14598 0.382 6.35 0.22 6.13 0.33
10 0.16380 0.17328 0.416 6.32 0.18 6.14 0.32

10 a 0.16380 0.17328 0.416 6.32 0.20 6.12 0.34
may be 0.01 unit in each case, or even 0.02 for calorimetric ob-
servations. The change in pK’ with variation of ionic strength
was then plotted against d;, and the curve drawn through the
points was extrapolated to zero ionic strength. This was done
for each salt used to vary the ionic strength. The results are
TABLE XII.
Born-Cresol Purple pK’ Change with Increase of Ionic Strength by Means
of Sodium Sulfate. Calorimetric Readings with
Indicator Concentration = 0.00003 by-.
-
Composi-
tion: Colori-
phosphate Electrc-
metric metric PK’
?iP as in
Sample 3,
CL 4 P=H+. olor ratio: i ndioator A pK’
Table IX, log R.
t N&04.
-- .-
pa ks.HnC
1 0.00000 0.00946 0.097 6.65 0.29 6.36 0.10
la 0.00000 0.00946 0.097 6.66 0.29 6.37 0.09
2 0.00270 0.01754 0.132 6.61 6.32 0.14

0.29
2a 0.00270 0.01754 0.132 6.61 0.28 6.33 0.13
3 0.00539 0.02563 0.160 6.57 0.28 6.29 0.17

3a 0.00539 0.02563 0.160 6.57 0.28 6.29 0.17
4 0.00809 0.03371 0.184 6.55 0.27 6.28 0.18

4a 0.00809 0.03371 0.184 6.55 0.27 6.28 0.18
5 0.01348 0.04988 0.223 6.50 0.26 6.24 0.22

5a 0.01348 0.04988 0.223 6.51 0.27 6.24 0.22
6 0.01887 0.06605 0.257 6.47 0.26 6.21 0.25

6a 0.01887 0.06605 0.257 6.48 0.27 6.21 0.25
7 0.02426 0.08222 0.287 6.46 0.27 6.19 0.27

7a 0.02426 0.08222 0.287 6.45 0.26 6.19 0.27
8 0.03234 0.10548 0.325 6.42 0.25 6.17 0.29

8a 0.03234 0.10548 0.325 6.42 0.25 6.17 0.29
9 0.04043 0.13073 0.361 6.39 0.23 6.16 0.30

9a 0.04043 0.13073 0.361 6.38 0.23 6.15 0.31
10 0.04851 0.15499 0.393 6.36 0.22 6.14 0.32

10 a 0.04851 0.15499 0.393 6.36 0.22 6.14 0.32
given in Table XXIV. Considering the uncertainty attached to

such extrapolations from even the most dilute solutions with
which these experiments were performed, the agreement of pK for
the different solutions is fairly good. The average pK values
thus obtained were then used as the basis for calculating A pK’.
TABLE XIII.
Brom-Cresol Purple pK’ Change with Increase of Ionic Strength by Means
of Potassium Sulfate. Calorimetric Readings with
Indicator Concentration = 0.00003x.
Composi-
tion: Colori-
phosphate Eleotro-
metric metric PK’
%? as in
Sample 3,
P G PmH+. dor ratio: ndicator A pK’
Table IX, log R.
+ KzSOa.
‘wkg.HzO
1 0.00000 0.00948 0.097 6.66 0.30 6.36 0.10
la 0.00000 0.00948 0.097 6.66 0.30 6.36 0.10
2 0.00227 0.01629 0.127 6.62 0.30 6.32 0.14

2a 0.00227 0.01629 0.127 6.62 0.29 6.33 0.13
3 0.00454 0.02310 0.152 6.60 0.29 6.31 0.15

3a 0.00454 0.02310 0.152 6.60 0.29 6.31 0.15
4 0.00681 0.02991 0.173 6.57 0.28 6.29 0.17

4a 0.00681 0.02991 0.173 6.57 0.28 6.29 0.17
5 0.01135 0.04353 0.208 6.54 0.28 6.26 0.20

5a 0.01135 0.04353 0.208 6.56 0.27 6.29 0.17
6 0.01589 0.05715 0.239 6.51 0.27 6.24 0.22

6a 0.01589 0.05715 0.239 6.53 0.27 6.26 0.20
7 0.02043 0.07077 0.266 6.49 0.26 6.23 0.23

7a 0.02043 0.07077 0.266 6.49 0.26 6.23 0.23
8 0.02724 0.09120 0.302 6.46 0.25 6.21 0.25
8a 0.02724 0.09120 0.302 6.46 0.25 6.21 0.25
9 0.03905 0.11163 0.334 6.42 0.23 6.19 0.27

9a 0.03905 0.11163 0.334 6.44 0.24 6.20 0.26
10 0.04086 0.13206 0.363 6.39 0.22 6.17 0.29

10 a 0.04086 0.13206 0.363 6.41 0.23 6.18 0.28
11 0.04697 0.15038 0.388 6.40 6.18 0.28

12 0.05297 0.16838 0.410 6.38 6.17 0.29
-
TABLE XIV.
of Magnesium Chloride. Calorimetric Readings with
Cotyoyi-
phosphke Electro- COlOri-
metric PK’
88 in LL 4 metric
01or rat.io: ndicator A pK’
Sample 3, PaH+.
Table IX, log R.
+ MgC12.
per kg.HzC
1 0.00000 0.00948 0.097 6.63 0.28 6.35 0.11
la 0.00000 0.00948 0.097 6.64 0.28 6.36 0.10

2 0.00329 0.01934 0.139 6.44 0.13 6.31 0.15
2a 0.00329 0.01934 0.139 6.44 0.12 6.32 0.14
3 0.00657 0.02918 0.171 6.30 0.04 6.26 0.20
3a 0.00657 0.02918 0.171 6.31 0.03 6.28 0.18
4 0.01094 0.04230 0.206 6.19 -0.05 6.24 0.22

4a 0.01094 0.04230 0.206 6.19 -0.07 6.26 0.20
5 0.01641 0.05871 0.242 6.09 -0.13 6.22 0.24
5a 0.01641 0.05871 0.242 6.10 -0.15 6.25 0.21
6 0.02298 0.07840 0.280 6.01 -0.18 6.19 0.27

6a 0.02298 0.07840 0.280 6.01 -0.18 6.19 0.27
7 0.02954 0.09810 0.313 5.92 -0.22 6.14 0.32

7a 0.02954 0.09810 0.313 5.95 -0.23 6.18 0.28
8 0.03939 0.12764 0.357 5.85 -0.26 6.11 0.35
8a 0.03939 0.12764 0.357 5.87 -0.27 6.14 0.32
9 0.04923 0.15715 0.396 5.80 -0.30 6.10 0.36
9a 0.04923 0.15715 0.396 5.81 -0.30 6.11 0.35
10 0.05908 0.18670 0.432 5.75 -0.35 6.10 0.36

10 a 0.05908 0.18670 0.432 5.75 -0.33 6.08 0.38
In Figs. 2 to 4, curves were drawn through the experimental

points determined for each salt, and all were extrapolated to
the same average pK value.
TABLE XV.
qf Magnesium Sulfate. Calorimetric Readings with
Composi-
tion: Cdori-
phosphate Electro-
as in metric metric PK'
P olor ratio: Idicator. A pK’
Sample 3. PaH+. log R.
rable IX,
+ MgSOh.
per kg.HzO
1 0.00000 0.00948 0.097 6.65 0.28 6.37 0.09

la 0.00000 0.00948 0.097 6.63 0.27 6.36 0.10

2 0.00227 0.01857 0.136 6.51 0.17 6.34 0.12
2a 0.00227 0.01857 0.136 6.51 0.16 6.35 0.11
3 0.00455 0.02766 0.166 6.41 0.10 6.31 0.15

3a 0.00455 0.02766 0.166 6.41 0.09 6.32 0.14
0.00758 0.03978 0.199 6.32 0.03 6.29 0.17

0.00758 0.63978 0.199 6.32 0.03 6.29 0.17
0.01136 0.05493 0.234 6.25 -0.04 6.29 0.17

0.01136 0.05493 0.234 6.25 -0.02 6.27 0.19
6 0.01591 0.07311 0.270 6.18 -0.08 6.26 0.20

6a 0.01591 0.07311 0.270 6.18 -0.07 6.25 0.21
7 0.02045 0.09130 0.302 6.13 -0.11 6.24 0.22

7a 0.02045 0.09130 0.302 6.13 -0.12 6.25 0.21
8 0.02727 0.11856 0.344 6.06 -0.15 6.21 0.25

8a 0.02727 0.11856 0.344 6.07 -0.15 6.22 0.24
9 0.03409 0.14584 0.382 6.02 -0.18 6.20 0.26

9a 0.03409 0.14584 0.382 6.02 -0.17 6.18 0.28
10 0.04091 0.17312 0.416 5.97 -0.21 6.18 0.28

10 a 0.04091 0.17312 0.416 5.97 -0.20 6.17 0.29
DISCUSSION.
A search of the literature revealed only one paper containing

data which could be used in estimating the pK’ variation of these
indicators at different ionic strengths. Lepper and Martin (26)
studied the “salt error” of phenol red at 18”. They diluted

phosphate and bicarbonate buffers with water and NaCl solutions,
and determined pan+ electrometrically and calorimetrically.
Their calorimetric solutions were diluted 10 per cent, whereas the
electrometric samples were not. On the assumption that pK’ of
phenol red = 7.78 for the phosphate color standards they used,
the pK’ values at the different ionic strengths have been calcu-
lated from their Tables I to V, and are given in our Table XXV.
Fig. 5 indicates the correspondence of the two sets of studies.
The agreement is good at higher ionic strengths, but Lepper and
TABLE XVI.

Brom-&sol Purde pK’ at .2020” with Addition of Glucose. Calorimetric
Readin& with Indicator Concentration =-0.00006 M.
-7
- T
C;g,“p”‘-
phosphate Eleotro- cbloli-
metric PK’
%? a8 in a G metric
c olor ratio: indicator. A pK’
pmH+. log R.
kFl::“i
+ glucoseY.
--
0.01256 0.112 6.61 0.27 6.34 0.12

0.01256 0.112 6.62 0.27 6.35 0.11
0.01256 0.112 6.61 0.27 6.34 0.12
0.01256 0.112 6.60 0.26 6.34 0.12
0.01256 0.112 6.58 0.27 6.31 0.15
0.01256 0.112 6.59 0.25 6.34 0.12
0.01256 0.112 6.56 0.25 6.31 0.15
0: 01256 0.112 6.55 0.23 6.32 0.14
Martin’s results for phosphate mixtures alone do not fit in well

with the rest of the data.
Unit of Electrolyte Concentration.-The ionic strength principle
enunciated by Lewis and Randall (21) is to the effect that in
dilute solutions, the activity coefficient of an ion is a function of the
total ionic strength only. This principle has been questioned by
Bronsted and La Mer (20) and more recently by La Mer and his
collaborators (27, 28) for salts involving symmetrical and unsym-
metrical high valence types, but in general it seems to hold fairly
well for uni-univalent salts even in higher concentrations than
0.001 M. The ionic strength p is a unit of concentration which
takes into account the number and valence of the ions present
TABLE XVII.
Phenol Red pK’ Change at 20” with Increase of Ionic Strength by Means of
Sodium and Potassium Phosphates. Calorimetric Readings
with Indicator Concentration = 0.00002M.
-
SaN+Tle I- C ompcsition:
KHzPOa N~sHPOI
P 4
Electro-
metric
PaHf.
I Colori-
metric
color
ratio:
PK’
indica-
tor.
ApK
I I log R.
-I-.-/
M P@ M P@
kg.HirO kg.HzO
1 0.00039 0.00163 0.00527 0.073 7.64 -0.35 7.99 0.05
la 0.00039 0.00163 0.00527 0.073 7.63 -0.35 7.98 0.06
lb 0.00056 0.00145 0.00491 0.070 7.43 -0.53 7.96 0.08

2 0.00078 0.00325 0.01053 0.103 7.62 -0.33 7.95 0.09
2a 0.00078 0.00325 0.01053 0.103 7.63 -0.33 7.96 0.08
2b 0.00078 0.00325 0.01053 0.103 7.65 -0.32 7.97 0.07
2c 0.00112 0.00290 0.00982 0.099 7.45 -0.53 7.98 0.06
3 0.00116 0.00488 0.01579 0.126 7.61 -0.32 7.93 0.11

3a 0.00116 0.00488 0.01579 0.126 7.63 -0.33 7.96 0.08
3b 0.00169 0.00435 0.01472 0.121 7.44 -0.53 7.97 0.07
4 0.00193 0.00813 0.02632 0.162 7.61 -0.34 7.95 0.09

4a 0.00155 0.00650 0.02107 0.145 7.59 -0.34 7.93 0.11
4b 0.00155 0.00650 0.02107 0.145 7.60 -0.32 7.92 0.12
4c 0.00224 0.00580 0.01964 0.140 7.43 -0.53 7.96 0.08
5 0.00232 0.00976 0.03159 0.178 7.58 -0.34 7.92 0.12

5a 0.00232 0.00976 0.03159 0.178 7.58 -0.33 7.91 0.13
5b 0.00232 0.00976 0.03159 0.178 7.59 -0.34 7.93 0.11
5c 0.00336 0.00870 0.02944 0.172 7.39 -0.54 7.93 0.11
6 0.00402 0.01690 0.05474 0.234 7.55 -0.35 7.90 0.14

6a 0.00348 0.01464 0.04740 0.218 7.55 -0.34 7.89 0.15
6b 0.00348 0.01464 0.04740 0.218 7.56 -0.34 7.90 0.14
6c 0.00504 0.01304 0.04416 0.210 7.37 -0.55 7.92 0.12
7 0.00502 0.02113 0.06842 0.261 7.54 -0.36 7.90 0.14

7a 0.00464 0.01957 0.06333 0.252 7.52 -0.35 7.87 0.17
7b 0.00464 0.01957 0.06333 0.252 7.52 -0.35 7.87 0.17
7c 0.00464 0.01957 0.06333 0.252 7.54 -0.35 7.89 0.15
7d 0.00672 0.01740 0.05888 0.243 7.33 -Q.56 7.89 0.15
TABLE XVII-concluded.
Composition. Colori-
Electro- metric PK’
(r 4 metric color ndica- L pK’
KHzPOa NazHPO4 PaH+. ratio: tor.
log R.
___~~-
8 0.00579 0.02439 0.07895 0.281 7.51 -0.36 7.87 0.17

8a 0.00579 0.02439 0.07895 0.281 7.50 -0.36 7.86 0.18
8b 0.00579 0.02439 0.07895 0.281 7.51 -0.35 7.86 0.18
8c 0.00579 0.02439 0.07895 0.281 7.52 -0.36 7.88 0.16
8d 0.00840 0.02175 0.07360 0.271 7.31 -0.56 7.87 0.17
9 0.00696 0.02927 0.09475 0.308 7.50 -0.37 7.87 0.17

9a 0.00696 0.02927 0.09475 0.308 7.48 -0.37 7.85 0.19
9b 0.00696 0.02927 0.09475 0.308 7.49 -0.36 7.85 0.19
9c 0.00696 0.02927 0.09475 0.308 7.48 -0.37 7.85 0.19
9d 0.01008 0.02610 0.08832 0.297 7.26 -0.57 7.83 0.21
10 0.00804 0.03380 0.10946 0.331 7.47 -0.37 7.84 0.20

10 a 0.00850 0.03577 0.11579 0.340 7.46 -0.38 7.84 0.20
10b 0.00850 0.03577 0.11579 0.340 7.47 -0.36 7.83 0.21
10 c 0.00850 0.03577 0.11579 0.340 7.47 -0.37 7.84 0.20
10d 0.01232 0.03190 0.10802 0.329 7.26 -0.57 7.83 0.21
11 0.01004 0.04227 0.13683 0.370 7.45 -0.38 7.83 0.21

11 a 0.01004 0.04227 0.13683 0.370 7.43 -0.39 7.82 0.22
lib 0.01004 0.04227 0.13683 0.370 7.44 -0.37 7.81 0.23
11 c 0.01004 0.04227 0.13683 0.370 7.44 -0.37 7.81 0.23
12 0.01159 0.04877 0.15790 0.397 7.42 -0.38 7.80 0.24

12 a 0.01159 0.04877 0.15790 0.397 7.42 -0.39 7.81 0.23
12 b 0.01159 0.04877 0.15790 0.397 7.43 -0.35 7.78 0.26
12 c 0.01159 0.04877 0.15790 0.397 7.43 -0.37 7.80 0.24
12 d 0.01159 0.04877 0.15790 0.397 7.43 -0.37 7.80 0.24
12 e 0.01690 0.04346 0.14728 0.384 7.22 -0.58 7.80 0.24
in the electronic environment. Thus all salts are reduced to the

same basis of number and charges of the ions. Where the ionic
strength principle holds, individual differences in salt effects
vanish.
If we follow out the curves for brom-cresol purple (Fig. 6) when
the diluting salts are KC1 and NazS04, all of the ions being differ-
ent in kind, and the salts in valence type, it is apparent that the
TABLE XVIII.
Sodium Chloride. Calorimetric Readings with
-
Cy;pai-
phospdate Electro- COlOri-
metric metric PK’
as in P ulor ratio: ndicator A pK’
Sample 3, PaH+. log R.
‘able XVII,
+ N&l.
per kg.H,O
1 0.00000 0.01575 0.125 7.61 -0.32 7.93 0.11
la 0.00000 0.01575 0.125 7.64 -0.33 7.97 0.07
lb 0.00000 0.01575 0.125 7.59 -0.34 7.93 0.11

2 0.00905 0.02480 0.157 7.59 -0.33 7.92 0.12
2a 0.00905 0.02480 0.157 7.57 -0.34 7.91 0.13
3 0.01810 0.03386 0.184 7.54 -0.34 7.88 0.16

3a 0.01810 0.03386 0.184 7.56 -0.34 7.90 0.14
3b 0.01810 0.03386 0.184 7.54 -0.35 7.89 0.15
4 0.02716 0.04292 0.207 7.51 -0.35 7.86 0.18

4a 0.02716 0.04292 0.207 7.52 -0.36 7.88 0.16
5 0.04528 0.06106 0.247 7.47 -0.37 7.84 0.20

5a 0.04528 0.06106 0.247 7.48 -0.38 7.86 0.18
6 0.06343 0.07922 0.281 7.43 -0.40 7.83 0.21

6a 0.06343 0.07922 0.281 7.43 -0.40 7.83 0.21
7 0.08159 0.09738 0.312 7.40 -0.42 7.82 0.22

7a 0.08159 0.09738 0.312 7.40 -0.41 7.81 0.23
8 0.12466 0.353 7.36 -0.43 7.79 0.25

8a 0.12466 0.353 7.35 -0.43 7.78 0.26
9 0.13617 0.15197 0.390 7.32 -0.46 7.78 0.26

9a 0.13617 0.15197 0.390 7.32 -0.45 7.77 0.27
10 0.16352 0.17934 0.423 7.29 -0.47 7.76 0.28

10 a 0.16352 0.17934 0.423 7.27 -0.48 7.75 0.29
variation in pK’ mainly depends on the concentration in terms of

&. The two curves are very close together for the two different
salts. However, if the molal unit of concentration is taken a
TABLE XIX.
Phenol Red pK’ Change at 20’ with Increase of Ionic Strength by Means of
Potassium Chloride. Calorimetric Readings with
- -c
Cotgyi-
Eleotxo- Colori-
phosphate metric
a8 in Ir metric PK’ A pK’
PaH+. :olor ratio: ndicator
rF$Y@1 log R.
f per kg.HxO
1 0.00000 0.01575 0.125 7.59 -0.36 7.95 0.09

la 0.00000 0.01575 0.12.i 7.60 -0.34 7.94 0.10

2 0.00905 0.02480 0.157 7.57 -0.34 7.91 0.13
3 0.01810 0.03386 0.184 7.54 -0.38 7.92 0.12

3a 0.01810 0.03386 0.184 7.55 -0.36 7.91 0.13
4 0.02716 0.04292 0.207 7.52 -0.39 7.91 0.13

4a 0.02716 0.04292 0.207 7.51 -0.37 7.88 0.16
5 0.04528 0.06106 0.247 7.48 -0.39 7.87 0.17

5a 0.04528 0.06106 0.247 7.48 -0.39 7.87 0.17
6 0.06343 0.07922 0.281 7.44 -0.39 7.83 0.21

6a 0.06343 0.07922 0.281 7.44 -0.40 7.84 0.20
7 0.08159 0.09738 0.312 7.41 -0.41 7.82 0.22

7a 0.08159 0.09738 0.312 7.42 -0.42 7.84 0.20
8 0.10886 0.12466 0.353 7.39 -0.43 7.82 0.22

8a 0.10886 0.12466 0.353 7.39 -0.43 7.82 0.22
9 0.13617 0.15197 0.390 7.33 -0.44 7.77 0.27

9a 0.13617 0.15197 0.390 7.35 -0.44 7.79 0.25
10 0.16352 0.17934 0.423 7.31 -0.45 7.76 0.28

10 a 0.16352 0.17934 0.423 7.32 -0.44 7.76 0.28
- -
great discrepancy arises. An apparent difference due to the kind

of salt used is obtained almost in the very beginning of the curves
at great dilutions.
It is clear that ionic strength is as closely correlated to variation
in the activity coefficients of these indicators as it is to variations
TABLE XX.
Sodium Sulfate. Calorimetric Readings with
Camposi-
tion:
phosphate Electrc- Colori-
as in metric metric PK’ A pK’
Sample 3 PaH+. olorratio: ldicator.
or 3b. log R.
‘able XVII
t NaaS0~
. per kg.HzC
1 0.00000 0.01579 0.126 7.62 -0.32 7.94 0.10
la 0.00000 0.01579 0.126 7.59 -0.33 7.92 0.12
lb 0.00000 0.01579 0.126 7.62 -0.32 7.94 0.10
1C 0.00000 0.01472 0.121 7.62 -0.53 7.95 0.09

2 0.00302 0.02485 0.158 7.60 -0.32 7.92 0.12
2a 0.00302 0.02379 0.154 7.40 -0.54 7.94 0.10
3 0.00537 0.03190 0.179 7.56 -0.32 7.88 0.16
3a 0.00604 0.03389 0.184 7.53 -0.35 7.88 0.16
3b 0.00604 0.03389 0.184 7.56 -0.35 7.91 0.13
3c 0.00604 0.03283 0.181 7.36 -0.35 7.91 0.13
0.00906 0.04295 0.207 7.54 -0.36 7.90 0.14
5 0.01343 0.05606 0.237 7.50 -0.35 7.85 0.19

5a 0.01509 0.06106 0.247 7.50 -0.36 7.86 0.18
5b 0.01509 0.05999 0.245 7.31 -0.56 7.87 0.17
6 0.01880 0.07219 0.269 7.45 -0.37 7.82 0.22
6a 0.02113 0.07916 0.281 7.48 -0.37 7.85 0.19
7 0.02417 0.08830 0.297 7.44 -0.38 7.82 0.22
7a 0.02717 0.09728 0.312 7.42 -0.38 7.80 0.24
7b 0.02717 0.09728 0.312 7.44 -0.37 7.81 0.23
7c 0.02717 0.09622 0.310 7.44 -0.57 7.81 0.23
8 0.03223 0.11247 0.335 7.42 -0.38 7.80 0.24

8a 0.03622 0.12445 0.353 7.39 -0.39 7.78 0.26
8b 0.03622 0.12445 0.353 7.42 -0.38 7.80 0.24
8C 0.03622 0.12339 0.351 7.22 -0.58 7.80 0.24
9 0.04028 0.13663 0.369 7.38 -0.39 7.77 0.27

9a 0.04528 0.15161 0.389 7.35 -0.40 7.75 0.29
9b 0.04528 0.15161 0.389 7.38 -0.40 7.78 0.26
SC 0.04528 0.15055 0.388 7.18 -0.60 7.78 0.26
10 0.04834 0.16079 0.401 7.36 -0.41 7.77 0.27

10 a 0.05433 0.17878 0.423 7.32 -0.42 7.74 0.30
225
TABLE XXI.
Potassium Sulfate. Calorimetric Readings with
- -
Cotyoyi-
phosphate Electro- c&g
SXllple 8,s in metric PK’ A pK’
CL
No. “;,“3”b” 3 P=H+. olor ratio: i ndioatm.
log R.
rable X+11
+ KzS04.
.- _-
Mr per kg.HnO
1 0.00000 0.01579 0.126 7.62 -0.34 7.96 0.08
la 0.00000 0.01579 0.126 7.59 -0.34 7.93 0.11
lb 0.00000 0.01472 0.121 7.42 -0.53 7.95 0.09

2 0.00227 0.02259 0.150 7.60 -0.35 7.95 0.09
2a 0.00227 0.02259 0.150 7.61 -0.34 7.95 0.09
2b 0.00227 0.02259 0.150 7.57 -0.34 7.91 0.13
2c 0.00227 0.02152 0.147 7.40 -0.54 7.94 0.10
3 0.00453 0.02938 0.172 7.57 -0.37 7.94 0.10

3a 0.00453 0.02938 0.172 7.59 -0.35 7.94 0.10
3b 0.00453 0.02938 0.172 7.55 -0.35 7.90 0.14
3c 0.00453 0.02832 0.168 7.38 -0.55 7.93 0.11
4 0.00679 0.03618 0.190 7.55 -0.38 7.93 0.11

4a 0.00679 0.03618 0.190 7.62 -0.27 7.89 0.15
4b 0.00679 0.03618 0.190 7.54 -0.36 7.90 0.14
4c 0.00755 0.03738 0.193 7.37 -0.56 7.93 0.11
5 0.01133 0.04976 0.223 7.52 -0.38 7.90 0.14

5a 0.01133 0.04976 0.223 7.59 -0.28 7.87 0.17
5b 0.01133 0.04976 0.223 7.52 -0.36 7.88 0.16
5c 0.01133 0.04976 0.223 7.51 -0.36 7.87 0.17
5d 0.01133 0.04870 0.221 7.33 -0.57 7.90 0.14
6 0.01586 0.06335 0.251 7.49 -0.39 7.88 0.16

6a 0.01660 0.06559 0.253 7.56 -4j.29 7.85 0.19
6b 0.01660 0.06559 0.253 7.50 -0.36 7.86 0.18
6c 0.01586 0.06335 0.251 7.50 -0.37 7.87 0.17
7 0.02039 0.07695 0.277 7.46 -0.40 7.86 0.18

7a 0.02265 0.08374 0.286 7.44 -0.39 7.83 0.21
7b 0.02265 0.08374 0.286 7.54 -0.30 7.84 0.20
7c 0.02265 0.08374 0.286 7.48 -0.37 7.85 0.19
7d 0.02039 0.07695 0.277 7.47 -0.37 7.84 0.20
- -
TABLE XXI-Concluded.
-
COtgP$
phosphate Electro- COlOri-
Sample a3 in metric metric PK’ A pK’
P
No. sgyt 3 PmH+. olor ratio : il ldioator.
log R.
‘1.‘able X+11
+ IMOP.
M w- kq.HgO
8 0.03019 0.10636 0.323 7.41 -0.39 7.80 0.24

8a 0.03019 0.10636 0.323 7.50 -0.31 7.81 0.23
8b 0.03019 0.10636 0.323 7.45 -0.37 7.82 0.22
8C 0.02718 0.09733 0.312 7.46 -0.37 7.83 0.21
9 0.03398 0.11771 0.343 7.39 -0.43 7.82 0.22

9a 0.03776 0.12907 0.355 7.39 -0.40 7.79 0.25
9b 0.03776 0.12907 0.355 7.47 -0.33 7.80 0.24
9c 0.03398 0.11771 0.343 7.43 -0.38 7.81 0.23
10 0.04077 0.13810 0.371 7.36 -0.44 7.80 0.24

10 a 0.04682 0.15625 0.391 7.37 -0.41 7.78 0.26
10 b 0.04682 0.15625 0.391 7.44 -0.34 7.78 0.26
10 c 0.04077 0.13810 0.371 7.42 -0.38 7.80 0.24
11 0.05588 0.18343 0.423 7.35 -0.42 7.77 0.27

11 a 0.05588 0.18343 0.423 7.40 -0.37 7.77 0.27
-
in the activity coefficients of the salts of simple organic and in-

organic acids. Whatever differences exist in the “salt errors”
caused by different salts at equal ionic strengths may or may not
be attributable to individual specific ion or molecule effects.
Individual Xpecijic Ion Effect.-To what extent specific ion
effects are present in these systems is not clear, nor may one decide
the question from these experiments alone. In Fig. 2, for brom-
cresol green, NaCl and KC1 follow along practically the same
curve as does the pair NazSOl and KzS04, and the pair MgC12
and CaClz; and this latter, in spite of the fact that MgCL has an
enormous effect, through hydrolysis, on the pan+ of buffer soutions
as compared with the other salts. The acetate mixture curve is
of a slightly different shape. The curves for the various salts
seem to show an indicator activity coefficient variation due to
valence type differences in the salts of the surrounding medium.
As the solution is more concentrated, the effects become more
pronounced. The glucose experiment (Table VIII), indicates a
TABLE XXII.
Magnesium Chloride. Calorimetric Readings with
Indicator Concentration = O.OOOO$
M.
-
Composi-
tion: C&Ii-
phosphate Electro-
metric metric PK’ A pK’
a8 in P
“%? olor ratio: Idicatm.
Sample 3, P&H+. log R.
‘able XVII
+ M&is.
.-
per kg.HzG
1 0.00000 0.01472 0.121 7.63 -0.31 7.94 0.10

la 0.00000 0.01472 0.121 7.61 -0.32 7.93 0.11

2 0.00327 0.02452 0.157 7.49 -0.43 7.92 0.12
2a 0.00327 0.02452 0.157 7.47 -0.45 7.92 0.12
3 0.00653 0.03432 0.185 7.37 -0.54 7.91 0.13

3a 0.00653 0.03432 0.185 7.36 -0.56 7.92 0.12
4 0.01089 0.04738 0.218 7.25 -0.64 7.89 0.15

4a 0.01089 0.04738 0.218 7.23 -0.66 7.89 0.15
5 0.01633 0.06370 0.252 7.15 -0.71 7.86 0.18

5a 0.01633 0.06370 0.252 7.14 -0.73 7.87 0.17
6 0.02286 0.08329 0.289 7.05 -0.77 7.82 0.22

6a 0.02286 0.08329 0.289 7.03 -0.77 7.80 0.24
7 0.02939 0.10288 0.321 6.99 -0.82 7.81 0.23

7a 0.02939 0.10288 0.321 6.97 -0.84 7.81 0.23
8 0.03918 0.13227 0.364 6.91 -0.88 7.79 0.25

8a 0.03918 0.13227 0.364 6.89 -0.89 7.78 0.26
9 0.04898 0.16165 0.402 6.85 -0.92 7.77 0.27

9a 0.04898 0.16165 0.402 6.83 -0.92 7.75 0.29
10 0.05877 0.19104 0.437 6.79 -0.96 7.75 0.29

10 a 0.05877 0.19104 0.437 6.77 -0.96 7.73 0.31
-
constant level of pK at constant salt concentration unaffected by

variation in sugar concentration.
Fig. 3~,for brom-cresol purple, is very much like that for brom-
cresol green; the relationships, however, are a little different.
TABLE XXIII.
Phenol Red pK’ Change at $0’ with Increase of Ionic Strength by Means of
Magnesium Sulfate. Calorimetric Readings with
Indicator Concentration = 0.00002 di.
-
cotyop-
Electro- C&Xi-
phosph’ate
metric metric PK’
as in
Sample 3,
P 4 PUH+. olor ratio: Idicatm. A pR’
? ible XVII log R.
t M&304.
.-
M per k,,.HtO
1 0.00000 0.01472 0.121 7.61 -0.32 7.93 0.11
la 0.00000 0.01472 0.121 7.60 -0.32 7.92 0.12

2 0.00226 0.02378 0.154 7.53 -0.41 7.94 0.10
2a 0.00226 0.02378 0.154 7.52 -0.41 7.93 0.11
3 0.00453 0.03283 0.181 7.45 -0.48 7.93 0.11

3a 0.00453 0.03283 0.181 7.46 -0.48 7.94 0.10
4 0.00754 0.04489 0.212 7.37 -0.55 7.92 0.12

4a 0.00754 0.04489 0.212 7.36 -0.55 7.91 0.13
5 0.01131 0.05998 0.245 7.28 -0.61 7.89 0.15
6 0.01659 0.08110 0.285 7.21 -0.67 7.88 0.16

6a 0.01659 0.08110 0.285 7.22 -0.68 7.90 0.14
7 0.02263 0.10524 0.324 7.13 -0.71 7.85 0.19
8 0.03017 0.13540 0.368 7.07 -0.76 7.83 0.21

8a 0.03017 0.13540 0.368 7.07 -0.76 7.83 0.21
9 0.03771 0.16558 0.407 7.01 -0.81 7.82 0.22

9a 0.03771 0.16558 0.407 7.01 -0.80 7.81 0.23
10 0.04676 0.20178 0.449 6.96 -0.84 7.80 0.24

10 a 0.04676 0.20178 0.449 6.96 -0.84 7.80 0.24
11 0.05582 0.23798 0.488 6.91 -0.88 7.79 0.25

11 a 0.05582 0.23798 0.488 6.90 -0.87 7.77 0.27
MgS04 shows a tendency (more pronounced in the case of phenol

red), to lower the pK’ curve. The glucose experiment (Table XVI)
showed no effect of the non-electrolyte, at least, in these con-
centrations. More concentrated sugar solutions would probably
230 indicator Activity Coefficients
TABLE XXIV.
Value of pK’ Indicator Extrapolated to p = 0.
Broom-cresol purple T Phenol

-
red.
Salt. PK Salt. PK Salt. PK
N&l 4.90 NaCl 6.46 NaCl 8.05

KC1 4.92 KC1 6.47 KC1 8.05
NazSOa 4.92 Na2S04 6.47 NazSOI 8.05
KzS04 4.91 K,SOa 6.46 KzSOd 8.05
NaGHzOz 4.93 PO4 6.47 PO4 8.02
MgClz 4.94 MgCl, 6.45 M&L 8.04
CaCL 4.95 MgS04 6.45 MgSCh 8.00
--
Average.. . 6.46

4.92 8.04
I I I I I 0 k+/
FIG. 2. The effect of varying concentrations of different salts on pK’ of

brom-cresol green.
affect the pK’ as found by the methods used in this work, by

causing a change in light absorption through the medium, and by
altering the dielectric constant of the solution, the non-electrolyte
exerting a salting-out effect.
p”‘I I I I I I.4 I I I I
6.1

0 005 0.2 0.15 02 025 03 03.5 04 0% 0.5
VF
FIG. 3. The effect of varying concentrations of different salts on pK’ of
brom-cresol purple.
I I I I i/
FIG. 4. The effect of varying concentrations of different salts on pKE of

phenol red.
TABLE XXV.
Data of Lepper and Martin ($6) Calculated to Show Phenol Red pK’ Change
at 18” with Increase of Ionic Strength.
-7-
-
Lwr Composition.
Eleotro c!olori-
#.Salt error” 1 pK’
Martin Ir G metric metric PaH+ (C) i ndica-
table Bllffer. salt. PaH+. PaH+. - PaH+ k’). tar.
NO.
.- pm-- -- _
I Phosphate.
1~/lOOO 0.002710.052 7.83 7.65 -0.18 7.96
IM/400 0.006800.082 7.81 7.66 -0.15 7.93
IM/150 0.018110.135 7.74 7.66 -0.08 7.86
1M/M 0.067910.260 7.65 7.61 -0.04 7.82
M/15 0.181060.425 7.55 7.55 *o.oo 7.78
_- ~-_-- .-

II Phosphate. NaCl
M/loo0 0.012870.113 7.76 7.62 -0.14 7.92
M/l00 0.021430.148 7.74 7.61 -0.13 7.91
~/32 0.043310.208 7.70 7.58 -0.12 7.90
~/16 0.075760.275 7.61 7.56 -0.0, 7.83
48 0.137630.371 7.53 7.53 ~0.00 7.78
- ~-
III Phosphate. NaCl
MC0 0.0256 0.160 7.51 7.36 -0.15 7.93
M/loo0 0.026640.163 7.50 7.36 -0.14 7.92
~/128 0.033500.183 7.45 ‘7.33 -0.12 7.90
~/32 0.05709 0.239 7.38 7.31 -0.07 7.85
M/16 0.089540.299 7.31 7.27 -0.04 7.82
703 0.151400.389 7.22 7.22 zto.00 7.78
--
IV Bicarbonate. NaCl
M/loo0 0.021120.145 7.50 7.37 -0.13 7.91
M/50 0.040220.20: 7.48 7.38 -0.10 7.88
M/16.6 0.0807 0.284 7.44 7.38 -0.06 7.84
M/6.9 0.1660 0.4Oi 7.42 7.41 -0.01 7.79
_- --~ _- --
V Bicarbonate. NaCl
0.040300.20 7.51 7.41 -0.10 7.88
M/30 0.07019 0.26 7.47 7.43 -0.04 7.82
M/lo 0.1409. 0.37., 7.44 7.43 -0.01 7.79
-
Phenol red curves (Fig. 4) present a slightly different picture.

The average slope is somewhat lower than for the brominated
methyl compounds, and all of the salts are much more closely
grouped. MgSO+ however, particularly at the lower concen-
trations, seemsout of line. La Mer and coworkers (27) have
found the same diihculty in working with salts of tri-trivalent
type.
0 a05 a2 aI5 a2 a25 w o.35 a4 a45 as
c-
FIG. 5. Comparison of data of Lepper and Martin with those of present

paper on change in pK’ of phenol red.
t;ir 0 am a2 0~5 0.2 025 03 a35 a4 a45 05
FIG. 6. The change in pK’ of brom-cresol purple with KC1 and NatSOl
plotted against concentrations on molal basis and on ionic strength basis.
233
The foregoing experiments were performed with dilute solutions
of acetate and phosphate mixtures. Although Lepper and Martin
(26) make a distinction between results obtained with bicarbonate
and phosphate buffers, their own data with NaCl (Fig. 5) in phenol
red solutions show very good agreement between solutions of these
two buffers. We did no experiments with bicarbonate buffer our-
selves, but there is little reason to believe that the results would
have been very different, provided the salt concentrations were
calculated on the ionic strength basis. In physiological solutions
the maximum concentration of about 30 mM bicarbonate would be
di = 0.16, where apparent individual salt or ion effects only

begin to come into play. However, if further work indicates a
real difference in effect of bicarbonate and phosphate, correction
figures would have to take into account the nature of the buffer.
Lepper and Martin’s curve for phosphate effect is quite different
from ours. Ours was established on the basis of 52 different
points, and fits in well with the curves for other salts.
The whole series of experiments shows no very consistent
specific ion or salt effects. For example, we find no common
effect of Mg++ ion in MgCI, and MgS04, or of SOh ion in KzS04,
Na2S04, and MgSO4.
Activity Coeficient Variation and Interionic Force E$ects.--We
have attempted to apply the equation of Debye and Hiickel
(Equation 8) to the curves of Figs. 2 to 4, but have not been com-
pletely successful in obtaining equations which would describe the
curves throughout their entire course. The whole of the ionic
dissociation and interionic attraction theory at the present time
is in such a state of flux (29,30) that we have attempted no modi-
fication such as would enable us to fit the data to the theory, or
vice versa. Nernst (31) and his coworkers (32, 33), on the basis
of the anomalous heats of dilution obtained with uni-univalent
strong electrolytes, advocate a return to the old Arrhenius in-
complete or partial dissociation theory, at the same time retaining
the Debye-Hiickel explanation for such effects as are due to in-
terionic forces. Bjerrum (34) also has put forward a slightly
different “association” explanation, and more recently (35) the
idea that the effective dielectric decreases in the immediate
neighborhood of the ions, thereby causing anomalous results.
Gronwall, La Mer, and Sandved (36) have expanded the Debye-
Hiickel formula in the form of an infinite series. They thereby
eliminate negative ion sizes and obtain positive values even in the
case of ions of small size. Simms (18), working with polyvalent
weak electrolytes, has attempted to correct for deviations from
the theory by taking into account a variable distance between
the two charges of a di-anion.
In general, the curves obtained in Figs. 2 to 4 conform approxi-
mately to the equation of Debye and Hiickel. Also, the corre-
spondence between these curves and some of those obtained with
weak acid buffer systems is very good. For example, the calcu-
lated curve of Cohn (16) based on the data of Sorensen, for the
second dissociation constant of phosphoric acid, and the curve for

the effect of NaCl on brom-cresol purple coincide almost exactly,
1.5&
and have the equation pK’ = pK -
l+ 1.654;
Also, there is here added proof of the dibasic character of these
indicators. The equation for a monobasic indicator, with the
assumption of a constant thickness of the ionic atmosphere =
0.33 X lo8 &, cm., would yield negative ion sizes. It is fairly
certain that such a result is not due to the same factors which
caused La Mer and his associates to expand the Debye-Htickel
equation, for here the ion sizes are quite large.
Gtintelberg and Schiodt (37) have recently published some
work in which they state that the behavior of the activity coefi-
cient of brom-phenol blue, the tetrabrom compound of the sulfon-
phthalein series, is that of a monobasic acid. However, if we
calculate from their single result at low concentrations, where
KC Ii’
ho corresponding to our z is given as 2.12 for a concentration of
KC1 = 0.1 N, pK’ = pK - 0.33, which corresponds almost exactly
to our results for brom-cresol purple and brom-cresol green. The
treatment of these indicators as dibasic is consistent with their
structure and known behavior.
Phenol red presents curves of a type somewhat different from
those of brom-cresol purple and brom-cresol green. For this,
we have no good explanation at the present time. Whether the
difference is due to large ion size, or the absence of the methyl and
bromide groups, we cannot say. Perhaps the results are due
to the same reason which caused the evaluation of 1.6 4; instead
of 2.0 4; for - log yoo; (15).
On the assumption of a constant value for the thickness of the

ionic atmosphere, 0.33 X lo* &J cm., we can make approximate
calculations for ion size at di = 0.4, this value changing with
different types of salt present, with the ratio of alkaline to acid
forms of the indicator, and with the concentration: from 5 to 8.7
X lo+ cm. for brom-cresol green and brom-cresol purple, and from
8.7 to 13.0 X 10d8 cm. for phenol red. These values are merely
speculative. Further developments in the theory of solutions,
and particularly those concerned with buffers and weak electro-
lytes, may make it necessary to revise our treatment of these
indicator anions, which, in structure at least, are so different
from the simpler substances on which the modern theories are

based. Furthermore, it must be remembered that not only
ionization but tautomerism equilibria are here involved. The
latter may not be affected to the same degree by electrostatic
forces.
Activity Coeficient Variation and Indicator Color.-The recent
work of Cohn and his collaborators on the phosphate and acetate
buffer system activity coefficients indicates that the mol fraction
&A
partition of the two members of the system, i.e. the ratio BA or
BA
--, may also enter in as a factor governing the magnitude of the
HA
activity coefficient at any one given ionic strength. This varia-
tion would be in accord with Briinsted’s specific ionic interaction
theory, Applied to these indicator studies, this would mean that
at any one given ionic strength, the pK’ of the indicator would
not be a constant, but would show some variation, depending
on the color, i.e. the ratio of alkaline to acid form of the indi-
cator, of the solution. Instead of one curve describing the varia-
tion of pK’ of the indicator with changing ionic strength, one
should obtain, for each salt studied (see Figs. 2 to 4), a family or
narrow sheaf of curves. The width of such a sheaf of curves
would be approximately the same for all salts, at the same ionic
strength, Each one of these curves of any one family of curves
would describe the pK’ variation with ionic strength change, for
the particular salt studied, at a constant ratio of alkaline to acid
form of the indicator; i.e., the curves would be isochromatic.
To obtain such isochromatic curves at varying values of log R
(the logarithm of the ratio of alkaline to acid form of the indicator),
the actual pan+ and the ionic strength of the particular salt solu-
tion used would progressively have to be so altered that the indi-
cator color remained constant. In otherwords, the change in p&u+
of the solution would have to be equal to, and of the same alge-
braic sign as the change in pK’ of the indicator. Such a nice ad-
justment is impossible for these studies, since the two variables
to.9
to.02 a.6
to.4
to.01

I I I I
c
CpK’ I 0.0
-0.2
-0.02 -0.3
-0.03 -0.4
-0.5
-0.04
-0.6
-0.05 -0.7
\\\ -0.8
-0.06
-0.9
-0.07gL 0.05 0.10 0.15 0.20 0.2:5
FIG 7. Correction chart for values of pK’ of the indicators at different

ionic strengths, when the ratio (R) alkaline to acid form of the indicator
varies. Adapted from Cohn’s (16) data on phosphate buffer mixtures.
are not known, but are to be observed or calculated. Hence the

curves given in Figs. 2 to 4 are not isochromatic nor do they cover
the possible variation of pK’ with ionic strength change between
the two extremes of color within which the indicators may be used.
The indicator, in its acid and alkaline form, constitutes a
buffer pair, and must so be treated. On the assumption that the
BAZ: BA or BA:HA ratio of an indicator affects the pK’ in the
same way that the mol fraction partition of phosphate and acetate
buffers influences their respective pK’ values, even when the indi-
cator concentration is as low as in our experiments, one may
correct for this factor in the following manner. Fig. 7 is inter-
polated from Cohn’s data on the second dissociation constant of
phosphoric acid, and applied to the indicators, which are also
regarded here as dibasic. The figure shows the correction cPxl,
to be applied to the pK’ value of the indicator at any ionic strength,
as the logarithm of the ratio of the alkaline to acid form of the
indicator varies. The experimentally determined pK’ values at
different ionic strengths, with different salts, have all been cor-
rected to the value at log R = 0, and are given in Tables XXVI to

TABLE XXVI.
Values of pK’ of Brom-Cresol Green at 20’ in Various Salts at Different
Ionic Strengths, When Log R = 0. Extrapolated pK at M = 0 Is 4.92.
N&l KC1 N&O4 KG304 C&12 M&h Acetate

B mixture.
0.025 4.77 4.77 4.78 4.79 4.75 4.73 4.78

0.050 4.72 4.71 4.74 4.74 4.69 4.67 4.73
0.075 4.68 4.67 4.70 4.70 4.65 4.63 4.71
0.100 4.65 4.65 4.68 4.68 4.62 4.60 4.69
0.125 4.63 4.63 4.66 4.66 4.59 4.58 4.67
0.150 4.61 4.62 4.64 4.64 4.57 4.56
0.175 4.59 4.61 4.62 4.63 4.56 4.55
0.200 4.57 4.59 4.60 4.61 4.53 4.52
0.225 4.56 4.59 4.59 4.60 4.52 4.50
0.250 4.55 4.58 4.57 4.59 4.51 4.49
XXVIII. These are the pK’ values to P ich cPKl is to be added

when the indicator color is such that log R is different from zero.
At the physiological ionic strength, p = 0.16, the corrections for
the indicator pK’ values given in these tables, would vary
throughout the useful range of the indicators, in the following
manner: for brom-cresol green, from +O.Ol to -0.03, for brom-
cresol purple, from +O.Ol to -0.02, for phenol red, from +O.Ol to
- 0.04, depending on the value of log R. At lower ionic strengths,
the corrections would, of course, be less. It is apparent from
Fig. 7 that this factor of the mol fraction partition is of much
less importance when the predominating color is that of the
alkaline form of the indicator.
The impossibility of systematically testing this effect for

indicators has already been mentioned. However, the probable
validity of such an effect for these substances also is indicated
by the table given by Hastings and Sendroy (24) in which such
consistency of pK’ for phenol red in ~/15 phosphate solutions
TABLE XXVII.
Values of pK’ of Brom-Cresol Purple at 20’ in Various Salts at Different
Ionic Strengths, When Log R = 0. Extrapolated pK at p = 0 Is 6.46.
NaCl KC1 N&30, KzSOa Phosphate

B M&h MgSo4 mixture.
_______~ ~_________
0.025 6.28 6.29 6.30 6.31 6.30 6 32 6.30

0.050 6.22 6.23 6.24 6.26 6.23 6.28 6.25
0.075 6.18 6.19 6.20 6.23 6.19 6.25 6.22
0.100 6.15 6.17 6.18 6.21 6.16 6.23 6.20
0.125 6.14 6.15 6.16 6.19 6.14 6.21 6.19
0.150 6.13 6.14 6.14 6.17 6.12 6.19 6.18
0.175 6.12 6.13 6.13 6.16 6.11 6.18
0.200 6.11 6.12 6.12 6.15 6.11 6.17
TABLE XXVIII.
Values of pK’of Phenol Red at .PO”in Various Salts at Different Ionic Strengths,
When Log R = 0. Extrapolated pK at p = 0 Is 8.04.
-
N&l KC1 N&O, KG301 M&12 MgSOa P hocphate
P 1mixture.
.- .-
0.025 7.91 7.93 7.92 7.93 7.93 7.94 7.93

0.050 7.86 7.87 7.87 7.88 7.89 7.91 7.90
0.075 7.84 7.86 7.85 7.85 7.86 7.89 7.87
0.100 7.82 7.84 7.82 7.83 7.84 7.88 7.86
0.125 7.80 7.81 7.80 7.81 7.82 7.87 7184
0.150 7.79 7.79 7.78 7.79 7.81 7.86 7.81
0.175 7.78 7.78 7.77 7.78 7.79 7.85 7.80
0.200 7.78 7.77 7.76 7.78 7.77 7.84 7.79
0.225 7.76 7.77 7.77 7.84
through the range of PCYn+from 6.84 to 7.98 was obtained. From

Table XXVIII one would expect the increase in P from 0.1200 to
0.1740 in their experiments, at constant color, to cause a progres-
sive decreasein pK’ indicator of about 0.04 unit. However, the
pan+ of the M/15 phosphates varied with the ionic strength, and the
consequent color change was such that log R varied from -0.94
at P = 0.120 to to.20 at p = 0.174. Fig. 7 indicates that be-
tween these limits the pK’ will progressively increaseby the same
amount; namely, 0.04 unit. The resultant of the two effects

would be the constant pK’ for phenol red obtained throughout
the whole range.
Results Applied to Calorimetric Estimation of p(~~+ of Salt
Solutions.-It is apparent that these indicators possess definite
physical characteristics which are much like those of other weak
acids or alkali buffer systems with their salts, and are affected in
approximately the same way by changes in the medium by which
they are surrounded. Hence it is no longer necessary to refer
to the “salt error,” when all that is meant is that the activity
coefficients of the colored anions, for the same general class of
salts, are different at different ionic strengths, and at different

proportions of the alkaline to acid form of the indicator.
In salt solutions of known ionic strength, one should be able to
estimate the pK’ of these indicators to within ho.02 unit, and to
determine pan+ with nearly the same accuracy. The “salt error,”
pcUn+(c) - pan+(e), has been a source of discrepancy, owing to
failure to allow for a predictable effect of interionic forces on the
apparent dissociation constants of the indicators in standard and
unknown solutions.
Practically, one may calculate, when using bicolor standards at
2U”,
(9) pcuH+ = pK’ of indicator at p + cPx, at log R of indicator + log R
of sample of sample at p of sample
where log R is the logarithm of the ratio of the alkaline to acid

form of the indicator, and $Kl is the correction in pK’ when log R
is not zero. The values pK’, in salt solutions of varying p, when
log R = 0, are found in Tables XXVI to XXVIII. The values of
crx’ when log R # 0 are found by referring to Fig. 7.
If instead of bicolor standards, standards with buffer and indica-
tor in the same solution are used, the assumedor electrometrically
determined pCXu+value of the standard buffer-indicator solution
also enters in :
(10) pcuH+ of = p”H+ of + pK’ of indicator + cpK, at log R of
sample standard at p of sample indicator at p of
sample
- pK’ of indicat.or - cpK, at log R of indicator

at P of standard at p of standard
For most purposes, the cpxt corrections of Equation 10 may be

neglected. Nevertheless, it is obvious that calorimetric readings
of salt solutions may be simplified and made more accurate by
using bicolor standards made up and marked in even color ratio
(log R) series, and calculating pan+ according to Equation 9.
Table XXIX is given to facilitate the preparation of such a series
of standards for any indicator.
Although these indicator dissociation constants have been
obtained at 20”, the results may also be applied to determinations
at 38” or at any intermediate temperature. In previous work
(24, 25), brom-cresol green was found to have practically no tem-

perature coefficient for pK’. Brom-cresol purple changed -0.10
unit and phenol red -0.13 unit in pK’ when the temperature was
increased from 20” to 38”. These temperature coefficients should
be the same throughout the ionic strength range from zero to p
= 0.2.
On the basis of these results, we may examine some previous
results in the field of calorimetric pan+ determinations. The pK’
for phenol red in ~/15 phosphate solutions at 20’ was found by
Hastings and Sendroy to be 7.78. For the same phosphate solu-
tions we obtain here a revised value of 7.80. This correction is
probably due to the actual change in pQn+ of the phosphates
(about +0.02 to i-0.01) when diluted 10 per cent, a refinement in
technique not used in previous determinations. In like manner,
the pK’ at 20” for brom-cresol purple previously found for the same
phosphate solutions would be changed from 6.19 to the value 6.21
found in the present work.
The acetates are not affected by dilution to the extent that
phosphates are. In fact, the results of the present determinations
show pK’ of brom-cresol green at 20” to be 4.67 for acetate solu-
tion instead of 4.72 for the ionic strength of 0.140. What this
discrepancy may be due to is not known. This indicator, as was
previously noted, is not always of constant purity.
In the development of a pan+ method for body fluids (24) we
previously noted that the ionic strength of the bicolor standards
(aside from the effect of salt on optical absorption) was of no
moment. This we can now better understand. If the acidity
and alkalinity of the two tubes are sufficient to keep the color of
the indicator in total acid and total alkaline form respectively,
TABLE XXIX.
Alkaline Form
Rounded Values of Log Acid ForrrL at Intervals of 0.05 or 0.1 pa H+ Unit
for
-
Use in Preparing Bicolor Standards.
-
Alkali tube.
I Acid tube.
I Log R.
Indicator. Alkali. Indicator. Acid.
cc. cc. cc. cc.

0.18 24.82 2.32 22.68 -1.10
.20 .80 .30 .70 -1.05
.23 .77 .27 .73 -1.00
.25 .75 .25 .75 -0.95
.28 .72 .22 .78 -0.90

.31 .69 .19 .81 -0.85
.34 .66 .16 .84 -0.80
.38 .62 .12 .88 -0.75
.42 .58 .08 .92 -0.70
.46 .54 .04 .96 -0.65
.50 .50 2.09 23.00 -0.60
.55 .45 1.95 .05 -0.55
.60 .40 .90 .lO -0.50
.66 .34 .84 .16 -0.45
.71 .29 .79 .21 -0.40
.77 .23 .73 .27 -0.35
.83 .17 .67 .33 -0.30
.90 .lO .60 .40 -0.25
.97 .03 .53 .47 -0.20
1.04 23.96 .46 .54 -0.15

.ll .89 .39 .61 -0.10
.18 .82 .32 .68 -0.05
.25 .75 .25 .75 0.00
.32 .68 .18 .82 +0.05
.39 .61 .ll .89 +0.10
.46 .54 .04 .96 +0.15
.53 .47 0.97 24.03 $0.20
.67 .33 .83 .17 $0.30
.79 .21 .71 .29 +0.40
.90 ..lO .60 .40 +0.50
2.00 23.00 .50 .50 $0.60

.08 22.92 .42 .58 $0.70
.16 .84 .34 .66 +0.80
.22 .78 .28 .72 +0.90
.27 .73 .23 .77 t-1.00
.32 .68 .18 .82 +1.10
regardless of how the indicator dissociation curve may be shifted
by some change in ionic strength or temperature, the bicolor
standards will always have the same color ratio. The conclusion
from our previous results on addition of salt to bicolor standards,
namely that the pK’ of phenol red would be 0.02 unit lower at zero
ionic strength than in ~/15 phosphate solution, is, of course,
erroneous.
The difference of -0.05 between calorimetric determinations of
dilute bicarbonate solutions at 20’ and 38”, given in the same
paper (24), was to be expected. The carbonic acid pK’, and
hence the actual pffn+ would be decreased 0.18 unit at the higher

temperature, while the indicator pK’ would decrease only 0.13
unit. The color reading would therefore be 0.05 unit lower.
CONCLUSIONS.
The data given in this paper represent, we believe, an advance

in the systematic tabulation of the experimental effect of salts
on the colors of three indicators widely used in biological work.
The practical application of these findings holds regardless of the
degree of validity of the theory involved.2
Until there is an extension, to other types of indicators, of this
method of studying the effect of salt concentration on indicator
color, it would be premature to advocate the application of these
theories to every indicator. All that may be stated at the present
time is that there are three indicators of the sulfonphthalein series,
which, on the basis of extensive experimental work, seem to behave
as do other typical weak electrolytes. The results are well in
accord with recent studies involving electrolyte behavior, and also
with Ostwald’s dissociation theory of indicator color.
2 As this paper is about to to go to press, we find that Kolthoff reports

(J. Physic. Chem., 32, 1820, December (1928)) the result of a study of the
“salt error” of several indicators, from which he concludes that the salt
correction of indicators cannot be adequately calculated from the equation
of Debye and Htickel. That the ionic strength of solutions alone is inade-
quate to account for the activity coefficients of ions in general is well
recognized. It seems from his results as well as those presented in this
paper that the treatment of “salt errors” as a problem of activity coeffi-
cients of weak electrolytes provides the best explanation for their existence
and magnitude.
We are indebted to Mr. Gilbert Stone for his careful determina-

tion of the electrometric pan+ values in this paper.
SUMMARY.
1. By means of electrometric pan+ estimations, and color

readings against bicolor standards, the effect of NaCl, KCl,
NazSO1, KzS04, MgCL, CaCL, MgSO+ acetate and phosphate
buffer mixtures, and glucose, on the activity coefficients of the
sulfonphthalein indicators, brom-cresol green, brom-cresol purple,
and phenol red, has been studied.
2. With the indicators, as with other weak acids in the presence
of their salts, the value of pK’ is dependent upon the total elec-

trolyte content of the solution. It is because of this fact that
addition of neutral salts alters the color of an indicator solution.
3. When the effects of salts on indicators are correlated with
ionic strengths, salts of different valence types show at the same
ionic strengths approximately like effects on the pK’ of the
indicator.
4. Quantitatively the relation between ionic strength and pK’ is
expressed by the equation of Debye and Hiickel, based on the
assumption that all the salts are completely dissociated and that
the combined effect of their ions on the log of an activity coeffi-
cient (in this case on the change they produce in pK’) is propor-
tional, as a first approximation, to the square root of the ionic
strength.
5. Our results indicate that other, lesser, factors than ionic
strength influence the relationship between pan+ and indicator
color. Among such factors may be varying specific interionic
effects of individual ions or groups of ions. Such effects are,
however, in most cases, relatively slight compared with the
main, non-specific effect indicated by the ionic strength.
6. Tables and equations are given for the determination of
pan+ calorimetrically, which take into account possible variations
in the salt content either of the sample or of the standards, or of
both. A correction is also applied for the ratio in which the
alkaline and acid forms of the indicator are present in solution.
7. The results are applied to a discussion of various phases of
recent work in calorimetric pan+ estimations.
J. Sendroy, Jr., and A. B. Hastings
BIBLIOGRAPHY.
1. Kiister, F. W., 2. anorg. Chem., 13,144 (1897).

2. VanCleeff, G. D., Rec. tram. chim. Pays-Bus, 20,198 (1901).
3. Acree, S. F., Am. Chem. J., 36,120 (1906).
4. von Szyszkowski, B., 2. physik. Chem., 68, 420 (1907); 63, 421 (1908).
5. Michaelis, L., and Rona, P., 2. Elektrochem., 14, 349 (1908); Biochem.
Z., 23, 61 (1909).
6. Sorensen, S. P. L., and Palitzsch, S., Compt. rend. Lab. Cadsberg., 9,
8 (1910).
7. Bjerrum, N., Die Theorie der alkalimetrischen und azidimetrischen
Titrierungen, Stuttgart, 1914.
8. Thiel, A., Sammlung chemischer und chemisch-technischer Vortrilge,
Stuttgart, 16, 307 (1911); 2. anorg. Chem., 132, 159 (1924).

9. Prideaux, E. B. R., The theory and use of indicators, London, 1917.
10. Michaelis, L., Hydrogen ion concentration, translated by Perlzweig,
W. A., Baltimore, 1926.
11. Kolthoff, I. M., Indicators, translated by Furman, N. H., New York,
1926.
12. Clark, W. M., The determination of hydrogen ions, Baltimore, 3rd
edition, 1928.
13. Bronsted, J. N., J. Chem. Sot., 119,574 (1921).
14. Stieglitz, J., J. Am. Chem. Sot., 26,1112 (1903).
15. Hastings, A. B., and Sendroy, J., Jr., J. Biol. Chem., 66,445 (1925).
16. Cohn, E. J., J. Am. Chem. Sot., 49,173 (1927).
17. Cohn, E. J., Heyroth, F. F., andMenkin, M. F., J. Am. Chem. Sot., 60,
696 (1928).
18. Simms, H. S., J. Physic. Chem., 32,112l (1928).
19. Debye, P., and Htickel, E., Physik. Z., 24,185 (1923).
20. Bronsted, J. N., and La Mer, V. K., J. Am. Chem. Sot., 46,555 (1924).
21. Lewis, G. N., and Randall, M., Thermodynamics and the free energy
of chemical substances, New York and London, 1923.
22. von Halban, H. V., and Ebert, L., Z. physik. Chem., 112,321 (1924).
23. Hastings, A. B., Murray, C. D., and Sendroy, J., Jr., J. Biol. Chem.,
71, 723 (1926-27).
24. Hastings, A. B., and Sendroy, J., Jr., J. Biol. Chem., 61,695 (1924).
25. Hastings, A. B., Sendroy, J., Jr., and Robson, W., J. Biol. Chem., 66,
381 (1925).
26. Lepper, E. H., andMartin, C. J., Biochem. J., 20,45 (1926).
27. La Mer, V. K., King, C. V., and Mason, C. F., J. Am. Chem. Sot., 49,
363 (1927).
28. La Mer, V. K., and Mason, C. F., J. Am. Chem. Sot., 49,410 (1927).
29. Tr. Far&y Sot., 23,334-544 (1927). The theory of strong electrolytes.
30. La Mer, V. K., Tr. Am. Electrochem. Sot., 61,631 (1927).
31. Nernst, W., Z. physik. Chem., 136,237 (1928).
32. Nernst, W., and Orthmann, W., Z. physik. Chem., 136,199 (1928).
33. Naudo, S. M., 2. physik. Chem., 136,209 (1928).
34. Bjerrum, N., Kgl. Dan&e. Vidensk. Selskab., Math.-jysisk. Medtl., 7,
No. 9 (1926).
35. Bjerrum, N., Tr. Farady Sot., 23,445 (1927).
36. Gronwall, T. H., La Mer, V. K., and Sandved, K., Physik. Z., 29, 358
(1928).
37. Giintelberg, E., and Schiijdt, E., 2. physik. Chem., 136,393 (1928).

THE ACTIVITY COEFFICIENTS OF
CERTAIN ACID-BASE INDICATORS
Julius Sendroy, Jr. and A. Baird Hastings
J. Biol. Chem. 1929, 82:197-246.
Access the most updated version of this article at

http://www.jbc.org/content/82/1/197.citation

Alerts:
• When this article is cited
• When a correction for this article is posted
Click here to choose from all of JBC's e-mail

alerts
This article cites 0 references, 0 of which can be

accessed free at
http://www.jbc.org/content/82/1/197.citation.full.ht
ml#ref-list-1

J. Biol. Chem.-1929-Sendroy-197-246 PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

J. Biol. Chem.-1929-Sendroy-197-246 PDF

Uploaded by

Copyright:

Available Formats

THE ACTIVITY COEFFICIENTS OF CERTAIN ACID-BASE

At an early stage in the development of the calorimetric method,

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

The theoretical aspects of indicator color change are sufficiently

f) ,,,,f) Ci&()Br Br~CX~ zaQBr Bg Y,,

’ I/;’ ’ I//O ’ j//O

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

The sulfonphthaleins are dibasic acids. However, the dissocia-

where K’ denotes the apparent stoichiometric dissociation con-

Also, from Equation 1,

and for a dibasic acid,

The ratio [BA] : [HA] may be altered by change of either

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

where y is the activity coefficient, v is the valence of the ion, and

(6) log y’ = 0.5 (v*2 - v12) 4

or for monovalent and divalent ions,

However, at higher concentrations, the ions must be regarded as

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

Procedure and Methods.

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

0 0.02 006 008 01 0.14

Ho25 salt per Liter

1 Acknowledgment should be made to the La Motte Chemical Company

1 0.00130 0.00303 0.00303 0.055 5.08 0.21 4.87 0.05

2 0.00260 0.00606 0.00606 0.078 5.06 0.24 4.82 0.10

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

3 0.00390 0.00909 0.00909 0.095 5.05 0.25 4.80 0.12

4 0.00650 0.01515 0.01515 0.123 5.04 0.26 4.78 0.14

5 0.01040 0.02424 0.02424 0.156 5.03 0.27 4.76 0.16

6 0.01427 0.03333 0.03333 0.182 5.03 0.27 4.76 0.16

7 0.01948 0.04545 0.04545 0.213 5.01 0.28 4.73 0.19

8 0.02468 0.05757 0.05757 0.240 5.01 0.29 4.72 0.20

9 0.03117 0.07272 0.07272 0.270 5.01 0 30 4.71 0.21

10 0.03896 0.09093 0.09090 0.301 5.01 0.31 4.70 0.22

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

3 0.01818 0.02424 0.156 5.03 0.26 4.77 0.15

4 0.02727 0.03333 0.182 5.01 0.27 4.74 0.18

5 0.04545 0.05151 0.227 5.00 0.28 4.72 0.20

6 0.06363 0.06969 0.264 4.98 0.30 4.68 0.24

7 0.08181 0.08787 0.296 4.97 0.31 4.66 0.26

8 0.10908 0.11514 0.339 4.96 0.32 4.64 0.28

9 0.13635 0.14241 0.377 4.94 0.33 4.61 0.31

10 0.16362 0.16968 0.412 4.93 0.34 4.59 0.33

0.21210 0.21816 0.467 4.93 0.36 4.57 0.35

When a ~/15 phosphate solution of about pq+ = 7.4, such as is

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

3 0.01818 0.02424 0.156 5.04 0.27 4.77 0.15

4 0.02727 0.03333 0.182 5.03 0.29 4.74 0.18

5 0.04545 0.05151 0.227 5.02 0.30 4.72 0.20

6 0.06363 0.06969 0.264 5.01 0.31 4.70 0.22

7 0.08181 0.08787 0.296 5.00 0.34 4.66 0.26

8 0.10908 0.11514 0.339 4.99 0.34 4.65 0.27

9 0.13635 0.14241 0.377 4.98 0.35 4.63 0.29

10 0.16362 0.16968 0.412 4.98 0.35 4.63 0.29

11 0.19998 0.20604 0.460 4.97 0.36 4.61 0.31

Downloaded from http://www.jbc.org/ by guest on April 15, 2019

3 0.00606 0.02424 0.156 5.05 0.26 4.79 0.13

4 0.00909 0.03333 0.182 5.04 0.27 4.77 0.15

5 0.01515 0.05151 0.227 5.01 0.28 4.73 0.19

6 0.02424 0.06969 0.264 5.01 0.30 4.71 0.21