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SHORT
COMMUNICATIONS
The calculation
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
144
SHORT
COMMUNKCATIONS
*()-
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
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.
.-_-_-_-____
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.
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
107.0+
10-J
10s*5=
102v4.
ZnL complexes
/Irtd.
1()9.06=
105.10
Acttr.
59 (1972)
SHORT COMMUNICX-IIONS
146
ft follows
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)
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.
2
3
4
5
6
A.
L.
A.
T.
J.
(Received
Awl.
12th October
1971)