143

SHORT

COMMUNICATIONS

The calculation

and use of a coefficients

Side-reaction
coefficients-usually
called r coefficients--are
nowadays widely
used in analytical
chemistry
to simplify equilibrium
calculations.
The concept of the
3~coefficient was originally
introduced
by Schwarzcnbach),
but several authors have
has susgcsted
that the influence
of practically
all
later extended
its USC. Ringborn
occurring
side reactions on a certain main reaction should be taken into account by
meuns of such coefficients. The net influence of several side reactions
is given by an
over-all Q cocflicicnt. which is often approximately
equal to the sum of the individual
u cacfficicnts.
If a metal ion M and a ligand L form a complex ML. hydrogen
or hydroxide
ions may affect the reaction in three ways. The reactions of the ligand with hydrogen
ions are taken into account
by the cocffrcicnt
the reactions
of M ions with
hydroxide
ion by the coefficient
%M(crt)and the reactions of ML with hydrogen
and
hydroxide
ions by the coefficient
c~+~r,,~~,
on). Analogously,
reactions
between L and
by the coefficients
CQ.,~,,,
interfering
cations,
Mt. M,,. . . ., arc taken into account
and
reactions
bctwcen
M
and
interfering
liyands.
A,,
A,,,
.
,.,
by
the
coef%M,,). - **
species responsible
for a side reaction
is
ficicnts zh)(&)~ zh((,,,,). . . . The interfering
always given in parentheses
in the subscript
of ~1.
The calculation
of x cocfficicnts
is, of course, based on equilibrium
constants.
For instance.
Iv
aJ.(Jf3r

where /In is the cumulative

protonation
constant
and N is the maximum
number of
bound protons.
Similar expressions
can bc written for other cycoefficients.
On the basis of these
coefficients,
conditional
stability
constants
of numerous
complexes
can be calculated-*.
An Q coefficient is thus the sum of a number of exponential
terms, and its caiculation
is actualiy a very simple mathematical
operation.
For calculating
cc coefas
a
function
of
pH
for
a
polybasic
acid),
modern
desk
calculators
ficients, (c~.{j.aI.(II)
and computers
arc particularly
appropriate
and are commonly
used.
Nevertheless,
the analyst often meets problems demanding
cccoefficients which
arc not tabulated
in any textbook,
and suitable calculators
or computers
are not
always immedi~ltely
available.
Moreover,
if many side reactions
occur, computers
do not always represent the most rapid and practical means of estimating
the values
of individual
and over-all cx cocffrcients.
The mason is that, as a rule, the final result
is affected by only a few of the numerous
side equilibria.
We have noticed that many chemists waste time by performing
calculations
withct coefficients in a far from rational way and arc not aware of the fact that additions
Aml.

Cltinr. Actu. 59 (1972)

144

SHORT

COMMUNKCATIONS

for subtr~~ctions~ of cxponcntiaf

terms can bc performed
by rcfcrcnce to short tables
often included in tables of logarithms.
Tables I and II arc given in a form particularly
appropriate
for chemists, who
generally
arc not intcrcstcd
in logarithmic
x values accurate
to more than two
dccimul pluccs. The tub& hardly need any explanation,
but a few comments
may be
appropriate.
If the sum of two cxponcntial
terms or their diffcrencc
is to be calculated with ;t precision
of two dccimnls
in the exponent.
the smafler term can be
neglected if the difference between the exponents
exceeds 2. When the exponents
differ
by more than one unit. tflc exponent
of the larger term will change at most 0.04. This
means that scvcral terms can bc neglected
in calculations
of individual
or over-alI
x cocfficicnts.
The USC of the tnblcs can best be illustrated
by means of a few cxamplcs.
Exmnple 1. Calculate
al.oit for the complexing
agent TTHA at pl-i 6.50. The
cumulative
protonation
constants
are log /j, = IO. 19. log [j, = 19.59. log /jX = 25.75,
log /f4 = 29.9 I ., log Ii 5 = 32.86, log &, = 35.28.
The complete
expression
for ~~~~~~~
is
~ ,.,,, )= 1 + IO->.
~~lO.l+
,o13.0
I(J.+
loIO.5
102575~
+

*()-

26.0

1()21.~1

,_

IO--

32.5

1()32.HC+

jo-

3J.O

10.2H

(2)

is immediately
seen that the third term, lO*. and the fourth term. 10f.25,
arc the two largest ones. The difference bctwcen their cxponcnts
is 0.34 and. accordIt

1AIJL.E

ADl~ll IOS 01:

0.0

IiSIONliNllAt.

II<I<.btS

t 0 .C t 0

=: to

((I

h)

0.3
0.4

0.301
0.254
0.212
0. I76
0.146

0.296
0.250
0.209
0.173
0.143

0.29 I
0.245
0.20s
0.170
0.140

0.286
0.24 1
0.201
0.167
0. I 37

0.28 1
0.237
0.197
0.lG.l
0. I35

0.277
0.232
0.194
0.160
0.132

0.272
0.228
0.190
0.157
0.129

0.267
0.224
0.187
0.154
0.127

0.263
0.220
0.183
0.151
0.124

0.25X
0.2fb
0.180
0. I48
0.122

0.5
Oh
0.7
0.8
0.9

0.119
0.097
0.079
0.064
0.05z

0.117
0.095
0.077
0.063
0.050

0.115
0.093
0.076
0.06 1
0.049

0.1 12
0.09 1
0.074
0.060
0.048

0.110
0.090
0.073
0.059
0.047

0.108
0.0X8
0.07 1
0.057
0.046

0.106
0.086
0.070
0.056
0.045

0.104
0.084
0.068
0.055
0.044

0.101
0.082
0.067
0.054
0.043

0.099
0.08 1
0.065
0.053
0.042

1.0
1.1
1.2
1.3
t .4

0.041
0.033
0.027
0.02 1
0.017

0.040
0.032
0.026
0.02 I
0.017

0.040
0.032
0.025
0.020
0.016

0.039
0.03 1
0.025
0.020
0.016

0.038
0.030
0.024
0.0 19
0.015

0.037
0.030
0.024
0.019
0.015

0.036
0.029
0.023
0.019
0.015

0.035
0.028
0.023
0.018
0.014

0.035
0.028
0.022
0.018
0.014

0.034
0.027
0.022
0.017
0.014

1.5
1.G
1.7
I.8

0.0 14
0.011
0.009
0.007

0.013
0.011
0.008
0.007

0.013
0.010
0.008
0.007

0.013
0.010
0.008
0.006

0.012
0.010
0.008
0.006

0.012
0.010
0.008
0.006

0.012
0.009
0.007
0.006

0.012
0.009
0.007
0.006

0.01 P
0.009
0.007
0.006

0.011
0.009
0.007
0.006

1.90,- 1.98

0.005

1.99-2.09

0.004

2.10-2.23

0.003

2.24 .2.46

0.002

2.47-2.94

0.001

0.1
0.2

~II-___--.---_____

Ard.

Chirrr. Accrr. 59 (1972)

.-_-_-_-____

SHORT

COMMUNlCATIONS

TABLE

(I -

12

145

II

f
0
1
4
2
3
._.. _-......__
- ___.._..
__. .._.__._.^
__..._..- ..__.._-_
.-. -_. __-.--.------.-----

6
-_---

.- --.-

7
8
.___.__.--_--__--__

9
0.728
0.45 1
0.312
0.227
0.170

0.687
0.433
0.302
0.220

1.643
0.6SO
0.416
0.292
0.2 14

1.347
0.6 17
0.401
0.283
0.208

1.176
0.587
0.386
0.274
0.202

1 .OSh
0.560
0.372
0.265
0.196

0.964
0.535
0.359
0.257
0.190

0.8X9
0.511
0.346
0 . .149
0.1X5

0.827
0.490
0.334
0.242
O.lpIO

0.5
0.6
0.7
0.8
0.5,

0.165
0.126
0.007
0.075
0.0%

0.160
0.122
0.094
0.073
0.057

0.156
0.119
O.OY2
0.07 1
0.056

0.152
0.116
0.0x)
0.070
0.054

O.l48
0.1 If
0.087
O.O6S
0.053

0.144
0.110
0.0x5
0.066
0.052

0.140
0.107
0.083
0.065
0.050

0.136
0.133
O.lo4
0.102
0.08 1 0.079
0.063
0.06 1
0.049
0.048

0.129
o.cm
0.077
0.060
0.047

I .o
1.1
1.2
1.3
1.4

0.046
0.036
0.028
0.032
0.018

0.045
0.03s
o.o2I(
0.022
0.017

0.044
0.034
0.027
0.02 I
0.017

0.04.7
0.030
0.026
0.02 I
0.016

0.0-12
0.033
O.WG
0.020
0.016

0.04 I
0.032
O.025
0.020
0.016

0.040
0.03 I
0.025
0.019
0.015

0,039
0.030
0.024
0.019
0.015

0.038
0.030
0.023
O.QlX
0.015

0.037
0.029
0.023
0.018
0.014

1.5
1.6
1.7
1.8
I.!)

0.014
0.0 1 I
0.00)
0.007
0.006

0.0 14
0.011
0.009
0.007

0.0 1 3
0.01 1
0.008
0.007

0.013
0.010
0.00x
0.006

0.013
0.010
o.Oot(
0.006

0.0 12
0.0 1O
0.008
0.006

0.012
0.010
0.008
0.006

0.012
0.009
0.007
0.006

0.012
0.009
0.007
0.006

0.01 I
0.009
0.007
0.006

1.91, I.98
__.

0.005

l.YY 2.w

0.004

2.10~224

0.003

2.25

0.002

2.47,.2.94

0.001

2.46

0.774
0.469
0.33
0.234
0.175

ing to Table I. tho sum of the two terms is 106~5~+o*1~=10f.7s. The other five terms
of eqn. (2) haveexponents more than 2 units smaller than thcexponent of this sum and
can thus be neglected.
Esuntple
2. What is the conditional constant of the zinc-DCTA
complex ut
pH 10 in the presence of free ammonia, [NH,] =O. 1 M, and sodium ions, [Na] =
0.2 = 1O-.7o M? Calculate pZn,,, if rt 10s3 M zinc salt solution is titrated.
The answer requires knowledge of the over-all a coefficients. The expressions
for the individu~ll coeff%5ents arc given below : the values of the constants needed were
taken from the collection in ref. 2, except KNu,,= 104*40 and fir = KI1,_= 103.7 of
DCTA (H,L). which are from a recent paper by Carr and Swartzfagcr, Kz,,t_ corrected by noting their new value of K,,,. is 1020.*4.
,,(,,, = 1 + lo- IO 101_3.17+
lo-20
1()1).37
+
10-30
1022.97
+
TX
+

lo-40

103.17.

1 f lo- O*O los.40 = 103~70.

al_(p&,f =

~X%nGufi,i =
a,,,,,,,

102S.48

f + I()- 1

1 -t- 1o-4

No constants
literature.

102.27

104.j+

10-2

Io-2

104.+

1014.j+

lo-

lo-*6

of basic or mixed ammonia

107.0+

10-J

10s*5=

102v4.

ZnL complexes
/Irtd.

1()9.06=

105.10

are given in the

C&t;.

Acttr.

59 (1972)

SHORT COMMUNICX-IIONS

146
ft follows

that the over-ail a coefficient

Eg+{f#,N;r)=103. + 103. - 1, i.e., acto Table 1, ai.= 103.70+0.1 = l()-x1. The over-all coefficient
azn(Nfg,.o)g)=
10. I. The conditional
constant
log Kc:;:- = 20. I - 3.8 - 5.1 = I 1.2, and if a 1O- ' M
solution is titrated, pZn,, = 4 (3 + 1 1.2) -t 5.1= 12.2. If the transition
point of the used
accuracy expressed as per cent error can
indicator,
pZnrrzlnu, is known, the attainable
be directly read from an error diagram (ref. 2, p_ 80).
Norc~. If the equilibrium
constants
valid at ~~=O.I wcrc corrected
to values
valid at the ionic strength of the solution (about 0.2-0.25). the pZn,,, value would be
about 0.1 unit lower.

cording

operations
It may also occur that other muthcmatical
terms huvc to be pcrformcd.
The following
tion ofexponcntiul
bc useful :
lo+
.---_--

10

lo-- IO

, 0 + s
--_.._
=
10 .- f

including
the subtracformula may sometimes

lo+

(3)

the stability constants

of the
In a papct from this laboratorya,
mononuclear
silver---TTHR complexes
wcrc dctcrmined
from pAg values. The vulue of
the stability constant
at pH 4.60 when pAg=2.72
(given in Table IX, Part II) was
corrected
by means of the expression
:
Correction

factor

4 CL -

= B C,+

CA61

EAsl

10-2.3010-2.72
= I0_->mgjj.-2.72

_
-

1o__%5

cr-h=0.42
and, according
to Tables I and II, x=0.140
and y=O.208. Conscqucntly,
we obtain IO-(O.14+0.21)= l()-().JS.
A chemist familiar with the USC of Tables I and II, ci\n easily and mentally
make such corrections
in a few moments.

Die ko~~r~)fl~sotrrerrisc~~l~
Ti/rcrtion. Ferdinand
Enkc, Stuttgart.
1955: c/I Ci. SCIIWAKCotrrpl~xontetric Tirrtrriotw.2nd Enyl. Ed., Mcthwn
& Co., London,
1969.
RINGIKIM. Cbnrpfescrtion br Ancri_vriculClwtrristry. Wiley-Intcrscicncc,
New York, 1963.
HARJU AND A. Rwciimhl.
ArmI. C&m. Acm, 49 (t970) 205.
RINCitlOhl AND L. HARJU. Attcil. C%iri?. Actit, 59 (1972) 33. 49.
A. E~O~IWIAN AND A. C. MARTELI.. imw~g,Cltcnr., 4 (1965) f 264,
D. UAlw AN11 I>. G. SWAI~W.VAGI~I~. rltxl. C/JCW.. 42 (1970) 1238.

G. SCWWARZENIIACI-I.

ZBNOACII AND H. FLASCI~KA,

2
3
4
5
6

A.
L.
A.
T.
J.

(Received
Awl.

12th October

Ci~ivr. Acta, 59 (1972)

1971)