10 Effect of Electrolytes on Chemical Equilibria

10A The Effect of Electrolytes on Chemical Equilibria

H3AsO4 + 3I- + 2H+ H3AsO3 + I3- + H2O
Added electrolyte: Ba(NO3)2, K2SO4, NaClO4; [I3-] , color
Fig. 10-1 Effect of electrolyte conc. on
conc.-based equilibrium constants.

K a' 105

K w' 1014

CKNO 3 concentration
Concentration NaCl, M
Fig. 10-2 Effect of electrolyte conc. on the
solubility of some salts.
10A-1 The Effect of Ionic Charges on Equilibria Fig. 10-2
10A-2 The Effect of Ionic Strength
1 2
ionic strength = = ([A ]Z A + [B]Z B2 + [C]Z C2 + )
2
[A], [B], [C], molar species conc.; ZA, ZB, ZC, ionic charge
Ex.10-1 Calculate the ionic strength of (a) a 0.1 M soln of KNO3 and (b) a 0.1 M soln
of Na2SO4.
1
(a) For KNO3 soln, = (0.1 12 + 0.1 12 ) = 0.1
2
1
(b) For Na2SO4 soln, = (0.2 12 + 0.1 2 2 ) = 0.3
2
Ex. 10-2 What is the ionic strength of a solution that is 0.05 M in KNO3 and 0.1 M in
Na2SO4.
1
= (0.05 12 + 0.05 12 + 0.2 12 + 0.1 2 2 ) = 0.35 M
2

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Effect of Charge on Ionic Strength (C = molarity of the salt)

Type 1:1 1:2 1:3 2:2

Example NaCl Ba(NO3)2, Na2SO4 Al((NO3)3, Na3PO4 MgSO4
C 3C 6C 4C

10B Activity Coefficients

aX : activity of species X
aX = X [ X ] [X] : molar conc.
X : activity coefficient
m n
for ppt Xm Yn, thermodynamic equilibrium constant : K sp = aX aY
K sp = [X] m [Y] n Xm Yn = K sp' Xm Yn
'
Concentration solubility product constant: K sp

10B-1 Properties of Activity Coefficients

Activity:
a measure of its effective conc. as
determined by the lowering of the
freezing point of water, by electrical
conductivity and by the mass action
effect.
1. x,
at moderate , x < 1,
As 0, x 1,
ax [X] and K sp' K .
sp
Fig.10-3 Effect of ionic strength on activity
coefficient.
2. x independent of the electrolyte, dependent only
3. For a giving , species charge x(departs farther from unity)
4. For a giving , x of ions of the same charge are approxi. equal.
5. x effective behavior in all equilibria in which it participates

HCN + H2O H3O+ + CN-

Ag+ + CN- AgCN(s)
Ni2+ + 4CN- Ni(CN)42-

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10B-2 The Debye-Hckel Equation
1923, P Debye & E. Hckel
0.51Z x2 Eq.10-5
log x = x = activity coefficient of the species X
1 + 3.3 x
Zx = charge on the species X
when << 0.01 1+ 1 = ionic strength of the solution
x = effective diameter of the hydrated ion
log x = 0.51Z x2 X in nanometers (10-9 m)
Debye-Hckel limiting law (DHLL)
Tab 10-1 Activity Coefficients for Ions at 25
Activity Coefficient at Indicated Ionic Strength
Ion
x, nm 0.001 0.005 0.01 0.05 0.1
+
H3O 0.9 0.967 0.934 0.913 0.85 0.83
+ -
Li , C6H5COO 0.6 0.966 0.930 0.907 0.83 0.80
+ - - - -
Na , IO3 , HSO3 , HCO3 , H2PO4 ,
0.4-0.45 0.965 0.927 0.902 0.82 0.77
H2AsO4-, OAc-
OH-, F-, SCN-, HS-, ClO3-, ClO4-, BrO3-,
0.35 0.965 0.926 0.900 0.81 0.76
IO4-, MnO4-
K+, Cl-, Br-, I-, CN-, NO2-, NO3-, HCOO- 0.3 0.965 0.925 0.899 0.81 0.75
+ + + + +
Rb , Cs , Tl , Ag , NH4 0.25 0.965 0.925 0.897 0.80 0.75
2+ 2+
Mg , Be 0.8 0.872 0.756 0.690 0.52 0.44
2+ 2+ 2+ 2+ 2+ 2+ 2+
Ca , Cu , Zn , Sn , Mn , Fe , Ni ,
0.6 0.870 0.748 0.676 0.48 0.40
Co2+, Phthalate2-
Sr2+, Ba2+, Cd2+, Hg2+, S2- 0.5 0.869 0.743 0.668 0.46 0.38
2+ 2- 2-
Pb , CO3, SO3 , C2O4 0.45 0.868 0.741 0.665 0.45 0.36
2+ 2- 2- 2- 2-
Hg2 , SO4 , S2O3 , CrO4 , HPO4 0.40 0.867 0.738 0.661 0.44 0.35
3+ 3+ 3+ 3+ 3+
Al , Fe , Cr , La , Ce 0.9 0.737 0.540 0.443 0.24 0.18
3- 3-
PO4 , Fe(CN)6 0.4 0.726 0.505 0.394 0.16 0.095
4+ 4+ 4+ 4+
Th , Zr , Ce , Sn 1.1 0.587 0.348 0.252 0.10 0.063
4-
Fe(CN)6 0.5 0.569 0.305 0.200 0.047 0.020

Ex.10-3 Use Eq. 10-5 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 Hg2+ obtained by interpolation of data
from Table 10-1.
0.51(2) 2 0.085
(1). log Hg =
2+ = 0.4016, Hg = antilog(-0.4016) = 0.397 0.40
2+
1 + 3.3(0.5) 0.085

(2). Table 10-1: = 0.100 Hg2+ = 0.38; = 0.050 Hg2+ = 0.46

0.015
Hg 2 + = 0.38 + (0.46 0.38) = 0.404 0.40
0.050
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10B-3 Equilibrium Calculations using Activity Coefficients
Ex. 10-4 Find the relative error introduced by neglecting activities in calculating the
solubility of Ba(IO3)2 in a 0.033 M solution of Mg(IO3)2. Ksp of Ba(IO3)2 is
1.57 10-9.
aBa 2 + a 2 = K sp = 1.57 109 = [Ba 2 + ] Ba 2 + [IO3- ]2 2 = K sp
IO3- IO3-
K sp
K sp' = = [ Ba 2 + ][ IO 3- ] 2
( Ba 2 + )( 2
IO 3-
)
1 1
= ([Mg 2+ ] 22 + [IO3- ] 12 ) = (0.033 4 + 0.066) = 0.099 0.1 M
2 2
Table 10-1: = 0.100 Ba2+ = 0.38; - = 0.77
IO3

1.57 10 9
K sp' = = 6.97 10 9 = [Ba 2 + ][IO3- ]2
0.38 0.77 2

[ IO 3- ] = 2 0.033 + 2 [ Ba 2 + ] 0.066
[Ba2+](0.066)2 = 6.97 10-9; [Ba2+] = solubility = 1.60 10-6
If neglect activities [Ba2+] (0.066)2 = 1.57 10-9; [Ba2+] = solubility = 3.60 10-7
3.60 10 7 1.60 10 6
relative error = 100% = 77%
1.60 10 6

Ex. 10-5 Use activities to calculate the [H3O+] in a 0.120 M HNO2 solution that is
also 0.050 M in NaCl. What is the relative percent error incurred by neglecting
activity corrections?
1
= (0.0500 12 + 0.0500 12 ) = 0.0500 M
2
= 0.050 = 0.85 ; NO - = 0.81; HNO 2 = 1.0
H 3O + 2

[H 3 O + ][ NO -2 ] K a HNO2 7.110 4 1.0

Ka = = =
( )( )
= 1.03 10 3
'

[HNO 2 ] H O+ NO- 0.85 0.81

3 2

[ H 3 O + ] = 0.120 1.03 10 3 = 1.11 10 2 M

If assuming all = 1: [H 3O + ] = 0.120 7.1 10 4 = 9.2 10-3

9.2 10 3 1.11 10 2
relative error = 100% = 17%
1.11 10 2

10B-4 Omitting Activity Coefficients in Equilibrium Calculations

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