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Chapter 9 Summary
Dr. Rahni
Analytical Chemistry
i) In the above figure, the molar solubility of the doubly charged ions
in BaSO4 increases by a factor of 2 in a solution of 0.02 M KNO 3
over a solution of pure water. On the other hand, the molar
solubility of a solution of Ba(IO3)2 with one singly and one doubly
charged ion only increases by a factor of 1.25 in a solution of 0.02
M KNO3 over a solution of pure water. And finally, the molar
solubility of AgCl with two singly charged ions only increases by a
factor of 1.2 in a solution of 0.02 M KNO3 over a solution of pure
water.
ii) The above chart shows that with ionic participants, the magnitude
of the electrolyte effect increases with charge.
Example 9-1
Calculate the ionic strength of (a) a 0.1 M solution of KNO 3 and (b) a 0.1 M
solution of Na2SO4.
(a) For the KNO3 solution, [K+] and [NO3-] are 0.1 M and
= 0.5([K+] ZA2 + [NO3-] ZB2)
= 0.5([0.1]12 + [0.1]12)
= 0.1
(b) For the Na2SO4 solution, [Na+] = 0.2 and [SO42-] = 0.1. Therefore,
= 0.5([Na+] ZA2 + [SO42-] ZB2)
= 0.5([0.2]12 + [0.1]22)
= 0.3
Example 9-2
What is the ionic strength of a solution that is 0.05 M in KNO 3 and 0.1 M in
Na2SO4?
= 0.5([K+] ZA2 + [NO3-] ZB2 + [Na+] ZC2 + [SO42-] ZD2)
= 0.5([0.05]12 + [0.05]12 + [0.2]12 + [0.1]22)
= 0.35 M
2) The ionic strength of a solution of a strong electrolyte consisting solely of
singly charged ions is identical with its total molar salt concentration. But
when the ions are no longer singly charged, the ionic strength increases.
Example
Ionic
Strength*
1:1
NaCl
1:2
1:3
2:2
Ba(NO3)2,
Na2SO4
Al(NO3)3,
Na3PO4
MgSO4
3c
6c
4c
3) For a solution with an ionic strength of 0.1 or less, the electrolyte effect is
independent of the kind of ions and dependent only on the ionic strength.
2)
ax =
[X]
is a
[X]m[Y]n =
K`sp
and
2)
3)
4)
5)
1)
2)
Table 9-1
Activity Coefficient at Indicated Ionic
Strength
Ion
x, nm
0.005
0.01
0.05
0.1
H+
0.9
0.934
0.913
0.854
0.825
(C3H7)4N+
0.8
0.932
0.911
0.847
0.816
(C3H7)3NH+,{OC6H2(NO3)3}
0.7
0.931
0.909
0.841
0.806
Li+,C6H5COO,(C2H5)4N+
0.6
0.930
0.906
0.833
0.795
CHCl2COO,(C2H5)3NH+
0.5
0.928
0.904
0.825
0.783
0.40.45
0.927
0.902
0.818
0.773
OH,F,HS,MnO4,IO4,HCOO
0.35
0.926
0.900
0.811
0.761
K+,Cl,Br,I,CN,NO2,NO3
0.3
0.925
0.898
0.806
0.753
Rb+,Cs+,NH4+,Tl+,Ag+
0.25
0.924
0.897
0.801
0.744
Na+,H2PO4,HCO3,HSO3,
CH3COO,(CH3)3NH+,C2H5NH3+
Mg2+,Be2+
Ca2+,Cu2+,Zn2+,Mn2+,Sn2+,
0.8
0.755
0.689
0.516
0.444
0.6
0.747
0.675
0.482
0.400
Sr2+,Ba2+,Cd2+,Hg2+,S2
0.5
0.742
0.668
0.463
0.376
Pb2+,CO32,SO32,MnO42
0.45
0.740
0.664
0.454
0.363
Hg22+,SO42,CrO42,HPO42
0.4
0.738
0.660
0.443
0.350
Al3+,Fe3+,Cr3+,La3+
0.9
0.538
0.442
0.241
0.177
{Co(H3NCH2CH2NH3)3}3
0.6
0.518
0.413
0.193
0.127
{OOCCOH(CH2COO)2}3
0.5
0.511
0.403
0.177
0.110
PO43,Fe(CN)63,{Co(NH3)6}3+
0.4
0.504
0.392
0.160
0.094
Th4+,Zr4+,Ce4+,Sn4
Fe(CN) 4
0.11
0.346
0.251
0.098
0.062
0.5
0.303
0.199
0.046
0.020
Ni2+,Co2+,Fe2+
(www.chemistry.msu.edu/courses/ cem834/Handouts/Handout4-ActivityCoef.doc)
Example 9-3
Use the Debye-Hckel equation to calculate the activity coefficient for
Hg2+ in a solution that has an ionic strength of 0.085. Use 0.5 nm for the
effective diameter of the ion. Compare the calculated value with
obtained by interpolation of data from Table 9-1.
= antilog (-0.0416)
Hg
2+
= 0.397 = 0.4
Table 9-1 indicates that
that
Example 9-4
Find the relative error introduced by neglecting activities in
calculating the solubility of Ba(IO3)3 in a 0.033 M solution of Mg (IO3)2.
The thermodynamic solubility product for Ba(IO3)3 is 1.57 X 10-9.
At the outset, we write the solubility-product expression in terms of
activities:
aBa2+ (aIO3-)2 = Ksp = 1.57 X 10-9
where aBa2+ and aIO3- are the activities of barium and iodate ions.
Replacing activities in this equation by activity coefficients and
concentrations yields
[Ba2+]
[IO3-]2
= Ksp
where
and
Ksp = Ksp/(
) = [Ba2+] [IO3-]2
= 0.38
= 0.77
Problem 9-8
-log X =
0.51 Z2X
1 + 0.33 X
a) Fe3+ at = 0.075
-log X =
= 0.20
= 0.64
c) Ce4+ at = 0.080
-log X =
= 0.073
= 0.088
Problem 9-13
1)
S = 3.1x10-8 = 1.8x10-4M
(b) Mh(OH)2
1)
S = 1.7x10-4M
2)
S = (7.1x10-12/4)1/3 = 1.2x10-4M
(c) BaSO4
1)
2)
S = 1.1x10-10/0.0167 = 6.6x10-9M
(d) La(IO3)2
1)
2)
S = (1.0x10-11/27)1/4 = 8x10-4M