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J . C . MCCOUBREY

747

SPECIFIC INTERACTION OF IONS

BY E. A. GUGGENHEIM
AND J. C. TURGEON
Chemistry Dept., The University, Reading

Received 8th September, 1954

After a thorough revision of the best values for ionic interaction coefficients in aqueous
golutions at 0" C and at 25" C, the theory of specific interaction has been applied quantitatively to several acid-base equilibria.
The formulae of Debye and Huckel 1 for the thermodynamic properties of
electrolyte solutions are based on the model of rigid ions with diameters all equal.
Sometimes one meets formulae of the same type with different values of the
diameter relating to different ions in the same solution, but such formulae contravene the requirements of thermodynamics. A modified set of formulae was proposed by one of us 2 having the following properties.

(i) They are thermodynamically mutually consistent.

(ii) They take account of the specific differences between electrolytes of the
same charge type present in the same solution.
(iii) They enable the thermodynamic properties of mixed electrolytes to be
deduced from those of single electrolytes.
(iv) They embrace Bronsted's 3 principle of specific interaction.
(v) They represent the facts with a useful degree of accuracy, at least for uniunivalent, bi-univalent and uni-bivalent electrolytes, up to an ionic
strength of about 0.1.
These formulae contain parameters called '. interaction coefficients " Is,, x for
cach combination of a cation R and an anion X. The value of each interaction
coefficient /?R,x is most simply determined fiom measurements on a solution
containing only the electrolyte whose ions are R and X. The values of /lR,x so
determined can then be used for estimating the thermodynamic properties of mixed
electrolytes.
Values of the coefficient / 3 R , x for numerous electrolytes in aqueous solution
have been determined 4 from the experimental data and have been tabulated.5
Most of the values being derived from freezing-point measurements, relate to
0" C . A few, derived from e.m.f. measurements, relate to 25" C or other
temperatures.
The main object of the present paper is to apply the theory to some experimental measurements of acid-base equilibria. It is, however, expedient at the

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748

SPECIFIC INTERACTION O F IONS

same time to revise the previously published values of the interaction coefficients.
The need for this arises from the following ca~ises.
(i) Whereas the interaction coefficients originally calculated nearly twenty
years ago related to activity coefficients and osmotic coefficients defined on the
mole fraction scale (" rational coefficients ") it is in fact customary to use activity
coefficients and osmotic coefficients defined on the molality scale (" practical
coefficients ") .
(ii) The most precise determination of the heat of fusion of ice leads to a value
of the cryoscopic constant of water slightly different from that formerly used.
(iii) Improved values of the general physical constants and of the dielectric
constant of water Iead to modified values of the fundamental coefficient in the
formulae of Debye and Huckel.
(iv) Thanks to isopiestic measurements we can now assign values to p at 25" C
for many mi-univalent electrolytes for which previously only values at 0" C had
been determined.
(v) The method of analyzing the experimental data has also been improved.
NOTATION

The following symbols will be used :

R, R'
cations,
x, X'
anions,
ZR = z,.
number of positive charges on cation,
- zx = z- number of negative charges on anion,
v+
number of cations per molecule of electrolyte,
Vnumber of anions per molecule of electrolyte,
v_
harmonic mean of v+ and v-,
mR
molality of cation,
mX
molality of anion,
m
molality of electrolyte,
ionic strength (on moIality scale),
I
activity coefficient (on molality scale) of electrolyte
YR,X
having cation R and anion X,
osmotic coefficient (on molality scale),
4
rx
fundamental coefficient in Debye-Huckel formulae,
interaction coefficient between cation R and anion X,
PR, X
A = a/In 10,
B EE 2$3/ln 10,
0
freezing-point depression,
coefficients in cryoscopic fonnula,
A, b
E
e.m.f .,
E"
standard e.m .f.,
KO
acidity constant,
Kw
ionization constant of water.
BASIC FORMULAE

We begin by quoting, without derivation, the basic formulae 6 relating to the

molality scale. The mean activity coefficient yR,x of the electrolyte having cation
R and anion X is given by

which for a solution of a single electrolyte reduces to

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749

E. A . G U G G E N H E I M A N D J . C . T U R G E O N

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where the subscripts R, X have been dropped. It is sometimes convenient to use

the corresponding formulae involving decadic logarithms, for example, for a
single electrolyte,
logy
where

= -

cc/ln 10,

= 2$/ln

10.

We shall use the osmotic coefficient 4 only in solutions of a single electrolyte.

It is then given by
1 - 4 = cc z+z-I*o(I+)- ypi11,
where

and tables of (T are availabIe.7

Values of the Debye-Huckel constant cc in water at various temperatures have
been calculated and tabulated.8 In particular :
at 0" C, A
at 25" C , A

= a/ln 10 = 0.4883 kg3 mole-%, 4 cc = 0.374 kga mole-),

a/ln 10 = 0.5085 kgs mole-*.

VALUES OF INTERACTION COEFFICIENTS

The revised values of the interaction coefficients calculated from measurements

on solutions of single uni-univalent electrolytes are collected in table 1. Columns
(a) contain values at 0" C obtained from measurements of freezing-point. Columns
(b) contain values at 25" C obtained from measurements of e.m.f. Column (c)
contains values obtained from isopiestic measurements relative to NaCl. Table 2
relates to bi-univalent and uni-bivalent electrolytes and, for the reason given later,
contains only values obtained from measurements of freezing-points. We shall
now indicate as briefly as possible how these values of /3 have been obtained.
TABLE1.+
(0)

electrolyte

k g mole-1

HCI
HBr
HI
HC104
HNO3
LiCl
LiBr
LiI
LiC103
LiC104
LiNO;
Li02CH
LiOAc
NaF
NaCl
NaBr
NaI
NaC103

0-25

VALUES FOR UNI-UNIVALENT ELECTROLYTES

0" c

(0)

(b)

ref.

a1

(b)
25"

kg mole-1

0.27
0.33

C
ref.

(4
25" C

kg mole-1

bl
b2
0-36
0.30

0.16
0.20
0.30

a2
a3
a3

0.25
0-35
0.23
0.1 1
0.19

a4
a4
a5
a6
a6

0.11
0.11
0.20

a3
a7
a3

a4

0.22
0.26
0.35
0.34
0.21

0.1 5

b3

0.18
0.07
(0.15)

0.17
0.21
0.10

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750

SPECIFIC INTERACTION OF IONS

TABLE1.-(contd.)
(0)

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electroIyte

0"

kg mole-]

NaC104
NaBrOj
NaI03
NaN03
Na02CH
NaOAc
NaCNS
NaH2P04
KF
KCl
KBr
KI
KC103

KBr03
KTO3

(a)

(6)

ref.

0-05

a4

-0.41

a8

-0.04
0.13
0-26

a5

0.05

0.04
0.00
0.06

kg mole-]

ref.

a9
a3, a10
all
a3
a4
a9
a4
a9

-0.43

a8
a9
a5
a10
a6
a6

-0.55
-0.55

-0.43
-0.26
-0.3 1
0.15

0.30

25" C

kg mole-1

0.13
0.01
0.04

a6
a6

-0.19
-0.30

KO;?CH
KOAc
KCNS
KH2P04
RbCl
RbBr
RbI
RbN03
RbOAc
CSCl
CsBr
CSI
CsN03
CsOAc
AgN03
TIC104

(6)
25" C

0.10

b4

0.23
0.20
- 0.06
0.13
0.10
0.1 1
0.15
-0.04

-- 0.07
- 0.07
- 0.1 1

- 0.14

b5

TI NO^

TlOAc

0.26
0.09
- 0.16
0.06
0.05
0.04
-0.14
0-26
0
0
-0.01
0.15
0.28
- 0.14
.- 0.17
- 0.36
- 0.04

(a) values at 0" C from freezing points.

(b) values at 25" C from e.m.f.
(c) values at 25" C from isopiestic measurements, relative to NaCI, by Robinson
and Stokes.
TABLE
2 . 4
electrolyte

BaC12
Ba(N03)2
coc12
K2S04

AND

VALUES OF BI-UNIVALENT AND UNI-BIVALENT ELECTROLYTES

FROM FREEZING POINTS

k g mole-]

0-7
-0.5
-t 1 . 1
0.1

ref.

0.8
-0.6
1-3
0.1

a8
a12
a8
a8

kg mole-]

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E . A. GUGGENHEIM A N D J . C . TURGEON

FREEZING
PoiNTs-The osmotic coefficient $ is calculated from the freezingpoint depression 0 by means of the formula
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S(1

+ be) = (v+ + v-)hm+,

where the cryoscopic constants A and b have the values (see appendix) :

b -- 4.8 x

1.860 deg. mole-1 kg,

We dcfine a quantity

+st

10-4

deg.-*

by
p t =

1 - $ cc z+z- I b ( 2 3 ) .

We then have

+ be) - (v+ + v-) Am@' (v+ + v-)hn?(+ - +st)

(v+ + v-)$?Xm2 = 2v+v-/3hm2,
if we plot S(l + be) - (v+ + v-)Amg!St against m 2 , we should
S(I

==

so that,
obtain a
straight line of slope 2v+v-/3h, from which /lcan be calculated. This procedure
is illustrated in fig. 1 which relates to measurements on KCl by Adams,9 by
2

0
-2

- 10
- 12-

1
0

20

30

40

50

60

70

80

90

100 1
0

120

lo"m2/mole2 kg-'
FIG. 1.

Scatchard and Prentiss 10 and by Lange,ll and to measurements on KC103 by

Scatchard, Prentiss and Jones12 and by Lange and Herre.13 The accuracy
attained in freezing-point measurements varies widely. An accuracy of i 0-0002"C
has been attained but rarely. We observe from fig. 1 that the three sets of measurements on KC1 are in fair agreement, but that in the case of KC103 there is a glaring
discrepancy since the two straight lines have slopes corresponding to ,B =- 0.19
kg mole-1 and - 0.30 kg mole-1. Adams 9 calibrated his thermocouple by
comparison with a 24 junction element calibrated by the Bureau of Standards.
Scatchard, Prentiss and Jones 12 calibrated their thermocouples against standardized platinum resistance thermometers. Lange,ll by contrast, states that he
calibrated his thermocouple against a Beckmann thermometer, calibrated at the
Reichsanstalt, at the KNO3 H20 eutectic (- 2-84' C) and at the K2Cx-207 H20
eutectic (- 0.63" C), but gives no details. Lange and Herre 1 3 give no information
at all about their calibrations and we consider them suspect. Until this discrepancy is cleared up we must reluctantly admit the possibility of other /3 values
being wrong by as much as 0.1 kg mole-1.

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752

S P E C I F I C I N T E R A C T I O N OF I O N S

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E.M.F.OF CELLS WITHOUT TRANSFERENCE.-we

on the e.m.f. measurements of the cell

shall illustrate the procedure

Pt, H2 I H a (m)1 HgzC12 I Hg

made by Hills and Ives 14 at 25" C. We define a quantity E"' by
E"'

aid
+ 2 RT
- Inn2 - 2 RT
--

F 1

+ nia

and we plot E"' against M , obtaining a straight line of intercept E" on the nz = 0
axis and of slope 2PRT/F, from which we calculate p. This plot is shown in fig. 2.
272

27I

72

71

270

70

2 69

69

>

60

268

lu
267

'

2 66

265

67

66

65

It is possible to draw a straight line from which only the points for the three
lowest concentrations and one other point below m = 0.1 mole kg-1 deviate by
more than 0.01 mV. This straight line leads to the value B = 0.228 kg mole-1
or p = 0.262 kg mole-1. By attaching greater weight to the three lowest concentrations we can obtain the alternative value B = 0.234 kg mole-1, or /3
= 0.269 kg mole-1.
These measurements are almost unique in their accuracy
and we consider them to be the only measurements which justify discussion of
the third significant figure in the value of /I.
According to the measurements of Harned and Ehlers 15 on the cell
Pt, H2 I HCl (n~)I AgCl 1 Ag

&.I,

is within their experimental error independent of temperature throughout

the range 0" C to 35" C and has the value /3 = (0.270 & 0.005) kg mole-1 or
B = (0.235 0*005)kg mole-1. These measurements also determine the standard
e.m.f. E". The value at 0" C is E" = 236.55 (abs) mV and at 25" C is E" = 222-5
(abs) mV.
Similar measurements by Harned, Keston and Donelson 16 on the cell

Pt, H2 I HBr

(172)

I AgBr 1 Ag

lead to the value /3 = 0.33 kg mole-1 or B = 0.29 kg mole-1 at 25" C and these
values are insensitive to temperature over the range 0" C to 25" C .

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E. A. G U G G E N H E I M AND J . C. T U R G E O N

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E.M.F.OF CELLS WITH TRANSFERENCE.-we

e.m.f. measurements of the cell

shall illustrate the method by the

made by Brown and MacInnes17 combined with measurements of the cation

transport number t f by Longsworth.18 The e,m.f. E of this cell is given by

FE

17iyf

- _ - 2 t + In _ _
RT
ldly"
where
denotes the value of tf averaged over the range In my from rn = rn'
to m = mr'. Provided this range is not too great this average is readily determined
by using rough values of y, or if necessary by successive approximation. Having
thus determined t',we calculate values of In (y'"''), and so for each value of rn
a vahe of k
log y , where k is an arbitrary unknown constant whose value will
be determined later. We plot

against m obtaining a straight line of slope B = 2P/In 10 with intercept k on the

= 0 axis. The plot is shown in fig. 3 in which the ordinate scale has been
adjusted so that k = 0.

14
12

1
0
A

0
4

2
0

5
6
7
1
0'm/mole kg-'

1
0

II

FIG.3.

VAPOUR
PREssuREs.-Isopiestic measurements cannot yet give accurate values
of the osmotic coefficient at molalities less than 0.1 and our formulae are not
valid at ionic strengths greater than 0.1. Consequently for uni-univalent electrolytes we can estimate values from the value of the osmotic coefficient at the
single concentration 0.1 mole kg-1 by means of the relation /3 = 104 - 9-19
at 25" C. Even so the experimental uncertainty in $ is at least 0.001 so that
the uncertainty in the derived value of p is at least 0.01 kg mole-1. Apart from
this uncertainty, we consider that there is a small systematic error in the values
of 4 at 25" C tabulated by Robinson and Stokes,l9 The isopiestic method gives
only relative values and therefore to obtain absolute values one has to assume
4 values for at least one standard substance. Robinson and Stokes, following
Robinson,aO assume that 4 = 0.932 for 0.1 molal NaCl at 25" C . This value
was obtained by applying the Gibbs-Duhem relation to activity coefficients

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754

S P E C I F I C I N T E R A C T I O N O F IONS

obtained by e.m.f. measurements. By the same procedure we find 4 == 0.934.

It is only a small difference, but it raises all the C$ values to the same extent and
so raises all /3 values by 0.02. As our source of 4 values at nz == 0.1 mole kg-1
we have used throughout the values tabulated by Robinson and Stokes,lY thus
corrected.* It should be noted that the 4 values for HCI and HBr in the tables
of Robinson and Stokes are derived from e.m.f., not isopiestic, measurements.
Their tables also include values for the alkali hydroxides obtained by extrapolation from e.m.f. measurements at higher molalities of cells containing
amalgam electrodes. These values are not much more than guesses and for the
purpose of our tables we disregard them.
For electrolytes other than mi-univalent the isopiestic measurements do not
extend down to an ionic strength 0.1 and consequently cannot yield useful estimates
of 18. For bi-univalent and uni-bivalent electrolytes the measurements of Robinson
and Stokes 19 extend down to a molality 0.1 which is an ionic strength 0.3. If
p values were estimated from these measurements they would be uncertain to
about & 0.1 kg mole-1 and we have not considered it worth while tabulating
such estimates. If required they are immediately obtainable by applying the
- 0.782) at molality 0.1.
formula /3 = 7.5 (c$
ACID-BASE EQUILIBRIA

Although the applicability of the theory of specific interaction to acid-base

equilibria was described by one of us,21 no previous detailed comparison is known
between our formulae and experimental measurements.
ACETICACID/ACETATE.-MeaSUrefnenfS Of e.m.f. Of the Cell
HOAc a
NaOAc b AgCl Ag,
P t y H 2 NaCI
c
where a, 6, c denote molalities and the ratios a : b : c were maintained constant,
have been made by Harned and EhIers.22 The e.m.f. E of this ccll may be
expressed in the form

! I

where Eo is the standard e.m.f. of the cell

Pt, H2 1 HCI I AgCl 1 Ag
and Ka is the acidity constant of acetic acid. Thc symbol h denotes the hydrogen
ion concentration and occurs as a small corrcction. Its value is thioughout these
experiments given with sufficient accuracy by
hh/a = K , = 1-7 x 10-5 molc kg-1.
We define E' by

If we plct E' against b r , we expect to obtain a straight line with intercept

E' - (RTIn KJF on the in = 0 axis and of slope

* Since submitting this text for publication we have had the advantage of an exchange
of views by correspondence with Prof. Robinson. We are now agreed that in one-tenth
molal sodium chloride the best value for 4 lies between 0.933 and 0.934 and that in onetenth molal potassium chloride the best value lies between 0.928 and 0.929. Values
for all other 1 : 1 electrolytes at this molality determined by the isopiestic method are
affected accordingly.

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E . A . GUGGENHEIM AND J . C . TURGEON

Thc measurements of Harned and Ehlers 22 cover a wide range of temperature.

We choose the measurements at 0" C because these can be correlated with freezingpoint measurements. The measured e.m.f.s have been converted from int. mV
to (absolute) mV and, according to Birge's values of the general constants,
(RT In lO)/F = 54.199 mV at 0" C. The computed values of E' have been plotted
against b + c in fig. 4. According to the freezing-point measurements on sodium
acetate and :odium chloride, we have
2
BNa, OAc - BNa, C1 = 2 j o (FNa, OAc - PNa, C1) =- 0.13 kg rn0le-l
a 1 1 d thc predicted slope of the straight line is
RT
hi 10
-- BNa, c1) = 54-2 x 0.1 3 mV kg mole-1
(BNa,

496.5

7.0 mV kg mole-1.

>

495.5

'

0-05

0.10

(b C)/mo I e kg'

FIG.4.

Thc line drawn in fig. 4 has this slope. From the intercept at
RT
E" - -In K, = 495.6 mV.

in =

0 we deduce

Wc also obtain from Harned and Ehler's measurements, converted to absolute

millivolts, E" = 236.55 mV. We deduce

E I n K,

= -

log K ,

= -

259.0,

259*0/54*199 - 4.779,
K , - 1-665 A 10-5 inole kg-1 for acetic acid at 0" C.
FORMtC AClD/FoRMATE.-MeaSUrementS
Of e.m.f. Of the CCII
H02CH a
Pt, Hz K02CH b AgCl Ag,
KCI
c !
wherc n, b, c denote molalities and
a = 0.80216 = 0.9268~ throughout,
have been made by Harned and Embree.23 Their measurements at 0" C have
been analyzed in a manner precisely analogous to those on acetic acid/sodium
acetate buffers. E' is plotted against b c in fig. 5. In the present case the
correction h is rather more important, but is readily evaluated by successive
approximations. According to the freezing-point measurements on potassium
foi mate and potassium chloride, we have
2
BK, OzCH - BK, CI = 2.30 ( F K , 02CH -- F K , C1) = 0.10 I<gmole-'

and the predicted slope of the straight line is

RT In 10
(BK,O ~ C H- BK,~ 1 ) 54.2 x 0.10 m V kg mole-'
F

5.4 mV kg rnolcl.

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756

SPECIFIC I N T E R A C T I O N OF I O N S

The line drawn in fig. 5 has this slope. From the intercept at m

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E" -nI:-

RT
-In

K,

log K,

K,

K,

0 we deduce

441-5 mV,

(236.5 - 441.5)mV

= -

205.0 mV,

205*0/54.199= - 3.782,
1.65 x 10-4 mole kg-1 for formic acid at 0" C .
= -

442.5

0.10

0.05
(b

+ c)/mle

kg-'

FIG. 5.

WATER/HYDROXIDE
IN PRESENCE
the cell

OF

cHLoR1DE.-Measurements

of e.m.f. of

where R denotes an alkali metal and a, b denote molalities, have been made by
Harned and his collaborators.24 The e.m.f. E of this cell may be expressed in
the form

where E" denotes the same standard e.m.f. as before and Kw is the thermodynamic
ionization constant of water. The term - 0.036 (a i
b) takes account of the
slight decrease in the activity of H20 as the total molality a b increases. We
define K ' by
HIE- E")
b
- In K ' = -___
Rr
+In-.

If we plot
-

log K' against c( 6 , we expect to obtain a straight line of' intercept

= 0 axis and of slope

log Kw on the in

2
-(/?R,oH - PR,CI 0-018 kg mole-1) = &,OH - B R , c ~ 0.016 kg mole-1.
I n 10
We use the measurements at 25" C . Having converted the e.m.f.s from int. mV
to mV we use the values (RT In lO)/H = 59.159 mV and E" = 222.5 mV. The
computed values of - log K' have been plotted against a b in fig. 6. In the
case of NaCl the measurements recorded for a b = 0.05 mole kg-1 in fact
relate 25 to a b = 0.06 mole kg-1. From the straight lines in fig. 6 we deduce
in the first place
log Kw= - 13.999, Kw = 1.002 x 10-14 mole2 kg-2,
and we consider this estimate more reliable than Harned's estimate 1-008 x 10-14.
From the slopes of the straight lines we obtain the values of PR, OH - /3R, c1 given
in the second column of table 3. In the third column of this table are given the
values of p ~~1 , obtained from isopiestic and e.1n.f. measurements. By addition
we obtain the values of FR, OH given in the fourth column. From these we have

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E . A . GUGGENHEIM A N D J . C . T U R G E O N

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TABLE3
R

pR,OHSR,Cl
kg mole-1

Li

-0.47

Na
K

cs

kg mole-1

PR,CI

PR,
OH
kg
mole-1

-0.05

0.22

-0.25

0.15

0.04

0.10
0

0.10
0.14

0.35

0-35

'$R, OH
m = 0-1

$R, OH
m=0.1
G and T

R and S

0894
0.929
0.933
0.954

0.920
0.925
0.944
0.942

calculated values of # for ROH at 0.1 mole kg-1 and these values are given in
the fifth column. In the sixth column we have given for comparison the values
tabulated by Robinson and Stokes.19 As already mentioned, these were obtained by extrapolation from e.m.f. measurements of cells with amalgam electrodes
and they can easily be wrong by 2 %.
14.04
14.03

14.02

I4 -01

<

14-00

13.99
13.98
13.97
13.96

13.95
0

4
6
8
1
0*m/m o Ie kg-'

1 0 1 2

FIG. 6.

WATER/HYDROXIDE
IN PRESENCE OF ~ ~ o ~ ~ ~ ~ . - - S imeasurements
milar
on cells
containing bromide instead of chloride have been made by Harned and Hamer.26
These cannot profitably be analyzed in exactly the same way because, whereas
E" for the chloride cell is known to within 0-1 mV there is for the corresponding
bromide cell a difference of about 0.5 mV between the value of E" found by
Harned and Hamer and that found by most other workers.27 Following
Harned and Hamer we can eliminate this uncertainty in E" by considering the
e.m.f. of the double cell
Pt' H2

1 EF

a
m-a

AgBr

I I
Ag

AgBr

HBr
a
RBr m-a

H2, Pt

where a = 0.01 mole kg-1 throughout and m is varied. The e.m.f. E of this cell
may be expressed in the form
FE
4171
- In Kw $- 0.036 I?? -1- In
i
In ?"'H+Y'OH-Y''Br---- ---11,
RT ==
??I - a
Y'Br_
I
_

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758

S P E C I F l C I N T E R A C T I O N O F IONS

where the single dash relates to the alkaline solution and the double dash to the
acid solution. We define K by
FE
a2m
2Am9
- log K = _____ - log ___
RTIn 10
m-a
1+m+
We have then
- log K
- log Kw f 0.016 m f
Br - &, Br) f m(BH, Br + BR, OH).
Consequently if we plot - log K against m we should obtain a straight line of
slope
(BH,Br BR,OH f 0.016 kg

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and of intercept
- log Kw a(&, B~ - BR, Br) at m = 0.
This intercept is not, as assumed by Harned and Hamer, equal to - log Kw
but differs from it by the small amount a(BR,B, - B H , B ~ ) . In fig. 7 the values
14-05

14.04
14.03

1402
0

14-01

I400
13.99

/
2
4
6

lo2m/mole

1
kq-

FJG.7.

of - log K are plotted against m for both sodium bromide and potassium
bromide. From e.m.f. the isopiestic measurements we know with amply sufficient
accuracy, since a = 0.01 mole kg-1,
a(&, Br - BN,, Br) = 0.01 x 0.12 = 0.0012,
a(BH, Br - B K , Br) = 0.01 x 0.17 = 0.0017.
The straight lines drawn have intercepts at nz = 0 corresponding to these values
when we assume for Kw the value obtained from the measurements in chloride
solutions. From the slopes in fig. 7 we deduce
PH, Br

PNa, OH =

PH,Br -k &,OH

0.36 kg mole-
0.45 kg

~ 0 3 3 kg mole-1 we obtain
Combining these with the e.m.f. value P H , B=
0.03 kg mole-1 as compared with the value 0.10 kg moIe-1 obtained
from the measurements in chloride solutions. Similarly we obtain PK, OH = 0.12
kg mole-1 as compared with the value 0.14 kg mole-1 obtained from the
measurements in chloride solutions.
Our final estimates for NaOH and KOH are
PNa, OH = (0-06 5 0.03)kg mole-1,
PK,OH = (0.13 0.03) kg mole-*.
From these we deduce at molality 0.1 the values YNa, OH = 0.765 and 1 ; ~OH
, = 0.776
and we believe these estimates to be incomparably more reliable than any based

PNa, OH =

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E. A . GUGGENHEIM A N D J . C. T U R G E O N

759

on e.m.f.s of cells with amalgam electrodes. It so happens that the estimate

made by Robinson and Stokes 19 is close to ours for NaOH but differs widely
for KOH.
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SOLUBILITIES

Bronsteds theory of specific interaction, of which the present theory is a

development, had as its main experimental basis solubility measurements. Details
can be found in Bronsteds 3 papers and we shall not recapitulate them.
Quite recently the theory has been applied28 with success to correlating the
solubility of AgCl in 0-0286 molal KNO3 determined by electrometric titration
by Brown and MacInnes29 with the thermodynamic solubility in pure water
determined from various e.m.f. measurements. An apparent small discrepancy
between these two quantities was thus shown to be spurious.
HEATS OF DILUTION

Our formulae provide a solid basis for analyzing measurements of heats of

dilution and correlating these with e.m.f. measurements over a range of temperature. They have recently been thus applied 30 to measurements on sodium
chloride.
IONIC ASSOCIATION

Our interaction coefficients take care of specific differences in the sizes, shapes
and polarizabilities of the ions. These are the specific properties which determine
the extent of ionic association, which we have hitherto not mentioned. Provided
the degree of association is small, our formulae are adequate to take care of it.
For uni-univalent electrolytes Davies 31 considers that B = 0.1 kg mole-1 is
characteristic in the absence of association. He regards B < 0.1 kg mole-1 as
evidence of association, but he does not give any views on B > 0.1 kg mole-1.
Possibly we may reinterpret Davies classification somewhat as follows :
B = (0.1 & 0.2) kg mole-1, association unimportant ;
B < - 0.1 kg mole-1, association important.
For bi-univalent and uni-bivalent electrolytes Davies regards B = 0.6 kg mole-1 as
characteristic in the absence of association, but according to this view the value
B = 1.1 kg mole-1 of CoC12 is not explained.
In bi-bivalent electrolytes association is much more pronounced and our
formulae are often not applicable. Davies32 views on the extent of association
in such electrolytes have been confirmed by recent freezing-point measurements
made in this laboratory by Prue and Brown on the sulphates of several bivalent
metals. Detailed discussion of these results must await their publication in the
near future.

We are grateful to Dr. J. E. Prue for many profitable discussions and to Dr.
M . L. McGlashan for constructive criticism.
APPENDIX
CRYOSCOPIC CONSTANTS OF WATER

We use the following notationTo

the freezing-point of pure water,
T - 0 the freezing-point of the solution,
AfH
the molar heat (enthalpy increase) of fusion of ice to pure
water at the temperature To,
Cl
molar heat capacity of liquid water (constant pressure) at To,
C,
molar heat capacity of ice (constant pressure) at To,
MI
the molar mass of water,
m
molality of solution.

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760
In the formula

SPECIFIC 1NTERACTlON OF IONS

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6(l
b0) == (v,
the constants A and b are defined by

+ v-)Am$,

We have the experimental values

AjH/Ml = (333.5 f 0.2)J g-1 at T T o (Osborne, J. Res. Nat. Bur. Stand., 1939,
23, 643),
RT" = 2.27115 x lO3J mole-1,
T" = 273.16" K,
Cl/M1 = 4.2176 J g-1 deg-1 (Osborne, Stimson and Ginnings, J . Res. Nat. Bur.
Stand., 1939, 23, 197),
C, = 9.055 x 4-1832 J mole-1 deg-1 (Giauque and Stout, J . Ainer. Chem. SOC.,
1936,58, 1144, with a small extrapolation).
From these we deduce
MiRT"2 2.27115 x 103 X 273.16 deg mole-1 kg
A = -103AfH 103 x 333.5
= (1.860 i 0.001) deg mole-1 kg.
Further we have
;=

so that
1
b=(2m6->%5

deg-1 = 4.8 x 10-4 deg-1,

and we notice that the value of b is about ten times smaller than might be expected owing
to fortuitous cancellation between the two terms.
We are not aware of any published computations of A or b during the past thirty years.
The values estimated by Lewis and Randall in 1923 are :
A = 1.858 deg mole-1 kg,
b = 5.3 x 10-4 deg-1.
TEXT

1 Debye

and Huckel, Physik. Z . , 1923, 24, 185.

2 Guggenheim, Rep. Scaiidinaviaiz Sci. Congr. (Copenhagen, 1929), p. 298 ; Phil.
Mag., 1935, 19, 588.
3 Bronsted, Kgl. Danske Vid. Selsk., Mat. fys. Medd., 1921, 4 (4) ; J. Amer. Chem.
Soc., 1922,44,877; 1923,45,2898.
4 Guggenheim, Phil. Mag., 1935,19, 588 ; 1936,22, 322.
5 Guggenheim, Thermodynamics (North-Holland Publishing Co., 1949), p. 3 18.
6 Guggenheim, Thermodynamics (North-Holland Publishing Co., 1949), $ 9.23.
7 Harned and Owen, Physical Chemistry of Electrolyte Solutions (Reinhold, 2nd ed.,
1950), p. 597.
8 Manov, Bates, Hamer and Acree, J . Amer. Chem. SOC.,1943, 65, 1766.
9 Adams, J. Amer. Chem. SOC.,1915, 37, 481.
10 Scatchard and Prentiss, J. Amer. Chem. SOC.,1933, 55,4355.
11 Lange, 2.physik. Chem. A , 1934,168, 147.
12 Scatchard, Prentiss and Jones, J . Amer. Chem. SOC.,
1934, 56,805.
13 Lange and Herre, 2.physik. Chem. A , 1938, 181,329.
1 4 Hills and Ives, J. Chem. SOC.,1951, 305, 311, 318.
15 Harned and Ehlers, J . Amer. Chem. Suc., 1932, 54, 1350.
16 Harned, Keston and Donelson, J. Amer. Chem. SOC.,1936, 58, 989.
17 Brown and MacInnes, J. Amer. Chem. SOC.,1935, 57, 1356.
18 Longsworth, J. Amer. Chern. Soc., 1932, 54, 2741.

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E . A . GUGGENHEIM A N D J . C . TURGEON

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19 Robinson and Stokes, Trans. Furaday SOC.,1949, 45,

20 Robinson, Trans. Roy. SOC.
N.Z., 1945, 75, 203.

76 1

612.

Guggenheim, Phil. Mag., 1935, 19, 639.

Harned and Ehlers, J . Amer. Chem. SOC.,1932, 54, 1350.
Harned and Embree, J . Amer. Chem. SOC.,
1934, 56, 1042.
24Harned and Copson, J . Amer. Chem. Soc., 1933, 55, 2206. Harned and Mannweiler, J. Amer. Chem. SOC.,1935, 57, 1873. Harned and Hamer, J. Amer. Chem.
SOC.,1933, 55, 2194. Harned and Schupp, J . Amer. Chem. SOC.,1930, 52, 3892.
25 Harned, private communication.
26 Harned and Hamer, J . Amer. Chem. SOC.,1933, 55,4496.
27 Janz and Taniguchi, Chem. Rev., 1953, 53,430.
28 Guggenheim and Prue, Trans. Furaday SOC.,1954, 50, 231.
29 Brown and MacInnes, J. Amer. Chem. Soc., 1935, 57, 459.
30 Guggenheim and Prue, Tram. Faraduy Soc., 1954, 50, 710.
32 Davies, Ann. Reports, 1952, 49, 30.
31 Davies, J . Chem. SOC.,1938, 2093.

21
22
23

TABLES

AND

a 1. Randall and Vanselow, J . Amer. Chem. SOC.,1924, 46, 2418.

a2. Hartmann and Rosenfeld, 2.physik. Chem. A, 1933, 164, 377.
a3. Scatchard and Prentiss, J. Amer. Chem. SOC.,1933, 55,4355.
a4. Scatchard, Prentiss and Jones, J. Amer. Chem. SOC.,1934, 56, 805.
a5. Scatchard, Prentiss and Jones, J . Amer. Chem. SOC.,1932, 54, 2690.
a6. Scatchard and Prentiss, J . Amer. Chem. SOC.,1934, 56, 807.
a7. Harkins and Roberts, J . Amer. Chem. SOC.,1916, 38, 2676.
a8. Hall and Harkins, J . Arner. Chem. SOC.,1916, 38, 2658.
a9. Lange and Herre, Z . physik. Chem. A, 1938,181, 329.
a10. Adams, J. Amer. Chem. SOC.,1915, 37,481.
a l l . Lange, 2.physik. Chem. A, 1934, 168, 147.
a12. Randall and Scott, J. Amer. Chem. SOC.,1927, 49, 647.

bl.
b2.
b3.
b4.
b5.

Hills and Ives, J . Chem. SOC.,1951, 305, 311, 318.

Harned, Keston and Donelson, J. Amer. Chem. SOC.,1936, 58, 989.
Brown and MacInnes, J. Amer. Chem. Soc,, 1935, 57, 1356.
Shedlovsky and MacInnes, J . Amer. Chem. SOC.,1937, 59, 503.
MacInnes and Brown, Chem. Rev., 1936, 18, 335.