Chapter 4

CONDITIONAL EQUILIBRIUM
CONSTANT OF REACTION
 SECONDARY EQUILIBRIUM
Definition
Main equilibrium: C + X 
(1)
 CX
( 2)

Solution of C and/or X might contain

other species
Secondary
Addition of other species into reaction equilibrium
mixture

Sec. Equil. [C]eq , [X]eq , [CX]eq change

affect

Main Equil. K or

2
 Conditional equilibrium constant
• [Xo]: Initial concentration of X
• [X’]: Concentration of X after main equilibrium
• [X]: Concentration of X after main and secondary equilibria
[X]’ = [X(Z)1] +…+ [X(Z)n] + [X]; knowing [X(Z)i] = [X].1,i.[Z]i

[ X ]o [X ']
  X (C ) and   X(Z)
[X '] [X ]

[X ' ] n
 X(Z)   1   1,i [ Z ]i
[X ] i 1

3
 Conditional equilibrium constant
If X is affected simultaneously by Z1, Z2:

C + X CX
+

Z1 Z2
↓↑ ↓↑
X(Z1).. X(Z2)..

Conditional eq constant of X:
n m
 X { Z 1, Z 2}  1   1,i [ Z1 ]i   1, j [ Z 2 ] j  X ( Z 1)   X ( Z 2 )  1
i 1 j 1

4
 Redox reaction
Effect of pH
Effect of complexation on redox half-equation
Effect of precipitation
Calculation of
 Conditional equilibrium constants
 Conditional equilibrium potentials
Effect of pH on redox half-equation
Half-equation:
Ox + ne- + m H+  Red + ½ m H2O
Nernst equation:
0,059  m 0,059 [Ox]
EE 0
lg[ H ]  lg (*)
n n [Re d ]

 If Ox + ne-  Red is affected by H+:

0,059 [Ox]
E  E '
0
lg (**)
n [Re d ]
 (*) and (**)  0,059
E ' E 
0 0
lg[ H  ]m
n
Effect of pH on redox half-equation
EX1:
Calculate conditional standard potential (Eo’) of following
half-equation at pH 1:
MnO4- + 5e- + 8H+  Mn2+ + 4H2O (Eo = 1,51 V)
Solution:

pH = 1  [H+] = 10-pH = 10-1 = 0,1 M

0,059  m 0,059
E ' E 
0 0
lg[ H ]  1,51  lg[10 1 ]8  1,42V
n 5
Effect of pH on redox half-equation
EX 2:
Determine oxidation ability of AsO43-/AsO33- at pH 8
(knowing that at pH 0, Eo’ = 0,57 V)
AsO43- + 2e- + 2H+  AsO33- + H2O
0,059
E ' E 
0 0
lg[ H  ]m
n
pH = 0, 0,059
E E 
0 0'
lg[ H  ]m  0,57 V
n
pH = 8, 0,059
E ' E 
0 0
lg[ H  ]m  0,1 V
n

=> Oxidation ability decreases as pH increases

Effect of complexation on redox half-equation
Generally, Ox + ne- Red
+ +
Z1 Z2
αOx(Z1)↓↑ αRed(Z2) ↓↑
Ox(Z1)1,… Red(Z2)1,…
Nerst’s equation:

0,059 [Ox] 0,059 [Ox' ]  Re d ( Z 2)

EE  0
lg E 
0
lg 
n [Re d ] n [Re d ' ]  Ox ( Z 1)

0,059 [Ox' ]
E  E '
0
lg
n [Re d ' ]
0,059  Ox ( Z1 )
E ' E 
0 0
lg
n  Re d ( Z 2 )
Effect of complexation on redox half-equation
 General expression:
Ox + ne- Red
0,059  Ox ( Z1 ) + +
E ' E 
0 0
lg (*)
n  Re d ( Z 2 ) Z1 Z2
αOx(Z1)↓↑ αRed(Z2) ↓↑
Ox(Z1)1,… Red(Z2)1,…

When Z1 (or Z2) is in excess compared to Ox (or Red):

 The most stable complex is formed (with the largest
number of ligands)
 Replace  in (*) with  of the most stable complex:
0,059  Ox
E0' E0  lg
n  Re d
 Effect of complexation on redox half-equation

EX: Calculate Eo’ of Fe3+/Fe2+ (Eo = 0,77 V) in presence of Y4-

(EDTA) with [Y4-] = 1M.
Solution

Since Y4- forms stables complexes with

both Fe3+ and Fe2+, so:
0,059  Fe 3 (Y )
E ' E 
0 0
lg
1  Fe 2 (Y )
0 .059 1    [Y 4
] 1  10 25 .1
E 0 '  0.77  lg FeY
 0.77  0.059 lg  0.13 V
1 1   FeY 2 [Y ]
4
1  1014 .3

In presence of EDTA, oxidative ability of Fe3+ decreases strongly

11
Effect of precipitation on redox half-equation
Generally, Ox + ne- Red
+ +
TOx(Z1) = [Ox].[Z1]
Z1 Z2
TRed(Z2) = [Red].[Z2]
↓↑TOx(Z1) ↓↑TRed(Z2)
Ox(Z1)↓ Red(Z2) ↓
Z2 + Ox(Z1)↓ + ne- Red(Z2)↓ + Z1
Nerst’s equation:
0,059 [Ox ] 0,059 TOx ( Z 1) [ Z 2 ]
EE 0
lg E 
0
lg 
n [ Kh] n TKh( Z 2 ) [ Z1 ] (*)
0,059 [ Z 2 ]
E  E '
0
lg (**)
n [ Z1 ]
0,059 TOx ( Z1 )
E ' E 
0 0
lg
(*) and (**) n TKh( Z 2 )
Effect of precipitation on redox half-equation
EX: Calculate Eo’ of Ag+/Ag (Eo=0.80 V) when [Cl-] = 10-3 M
Ag+ + e- Ag
-
+
AgCl + e Ag + Cl Cl
↓↑TAgCl
AgCl

0.059 TOx ( Z 1) TAgCl

E ' E 
0 0
lg  0.80  0.059 lg  0.21V
n TRe d ( Z 2) 1

0.059 [ Z 2 ] 1
E  E '
0
lg  0.21  0.059 lg 3  0.39V
n [ Z1 ] 10

 In presence of [Cl-] = 10-3 M, oxidative ability of Ag+ decreases

considerably
 Redox reaction
 Conditional equilibrium constants
n1 n2 ( E1o '  E 2o ')

K '  10 0 , 059

 Conditional equilibrium potentials

 Only Ox1/Red1 is affected by H+

n E o
 n E o
0.059
Eequiv’ = 1 1 2 2 + lg[ H  ]m
n1  n2 n1  n2
 Ox1/Red1 is affected by both H+ and another secondary
equilibrium
n E o
'  n E o
0.059
Eequiv’ = 1 1 2 2
+ lg[ H  ]m
n1  n2 n1  n2
 Redox reaction
 Conditional equilibrium potentials

 Both pairs are affected by H+ and secondary equilibria

’ n E o
'  n E o
2 2' 0.059
Eequiv = 1 1
+ lg[ H  ]m
n1  n2 n1  n2

 Ox1/Red1 is affected by H+ and have different

stoichiometric coefficients, both pairs are affected by
secondary equilibria
Ox1 + n1e + mH+ ⇄ p Red1 + ½ m H2O
n E o
'  n o
2 2'
E 0.059   m [Re d ]1 p 
’
Eequiv = 1 1
+ lg  [ H ] 
n1  n2 n1  n2  p 
 Redox reaction
EX1: Establish expression of equivalent potential in function of
H+ for the following reaction; effect of OH- on Fe3+, Fe2+ is
negligible.
MnO4- + 5Fe3+ + 8H+ = Mn2+ + 5 Fe3+ + 4H2O
Half-equation 1: MnO4- + 8H+ + 5e- = Mn2+ + 4H2O
Half-equation 2: Fe3+ + e = Fe2+
Only half-equation 1 is affected by H+

ETĐ’ = (1.51 x 5 + 0.77 x 1)/6 + 0.059/6 x lg[H+]8

 Redox reaction
EX2: Xét ảnh hưởng của H+ lên ETĐ của phản ứng sau nếu
xem xét ảnh hưởng của OH- lên Fe3+, Fe2+ và Mn2+ ở pH 3
MnO4- + 5Fe3+ + 8H+ = Mn2+ + 5 Fe3+ + 4H2O

Half-equation 1: MnO4- + 8H+ + 5e- = Mn2+ + 4H2O

+
OH-

Mn(OH)x
Mn(OH) = 1 + 1,1.[OH-]1 + 1,3.[OH-]3
= 1+ 103,9.[OH-] + 108,3.[OH-]3

E1o’ = 1,51 - 0,059/5lg(1/Mn(OH)) = 1,51 + 0,059/5lg(Mn(OH))

 Redox reaction
Half-equation 2: Fe3+ + e = Fe2+
+ +
OH- OH-

Fe(III)(OH) Fe(II)(OH)

Fe(III)(OH) = 1 + 1,1.[OH-]1 + 1,2.[OH-]2 + 1,3.[OH-]3

Fe(II)(OH) = 1 + 1,1.[OH-]1 + 1,2.[OH-]2 + 1,3.[OH-]3 +1,3.[OH-]4

E2o’ = 0,77 - 0,059/1.lg[(Fe(III)(OH))/(Fe(II)(OH))]

 Redox reaction

’ n E o
'  n E o
2 2' 0,059
Etđ = 1 1
+ lg[ H  ]m
n1  n2 n1  n2

E1o’ = 1,51 - 0,059/5lg(1/Mn(OH)) = 1,51 + 0,059/5lg(Mn(OH))

E2o’ = 0,77 - 0,059/1.lg[(Fe(III)(OH))/(Fe(II)(OH))]

 Redox reaction
EX3: Calculate E’ and K’ of the reaction between AsO43-/AsO33-
(E1o = 0.57 V) and I2/2I- (E2o = 0.54 V) at pH 0 and pH 8
 Redox reaction
EX3: Calculate E’ and K’ of the reaction between AsO43-/AsO33-
(E1o = 0.57 V) and I2/2I- (E2o = 0.54 V) at pH 0 and pH 8
Conditional equilibrium constants for acid-base,
complexation and precipitation reactions

 Effect of complexation on complexation reaction

 Effect of complexation on precipitation reaction

 Applications of conditional equilibrium constants in

Analytical Chemistry
Complexation reaction-Effect of complexation
Ta có [A’] = A(z1).[A] , [p’] = p(z2).[p] , [D’] = D(z3).[D]

A + p D
+ + +
Z1 Z2 Z3
αA(Z1)↓↑ αp (Z2) ↓↑ αD (Z3) ↓↑
A(Z1)1,... p(Z2)1,… D(Z3)1,…

Combination of secondary and main equilibrium:

A’ + p’  D’

[ D' ] [ D]  D( Z 3)  D( Z 3)  D( Z 3)
 '      ' 
[ A' ][ p' ] [ A][ p]  A( Z 1) p ( Z 2 )  A( Z 1) p( Z 2 )  A( Z 1) p( Z 2 )
Complexation reaction-Effect of complexation
EX: Calculate β’CuY2- at pH 5
Cu2+ + Y4- CuY2-
+ +
OH- H+
αCu(OH)↓↑ α Y(H) ↓↑
Cu(OH)1,… HY3-,…

Knowing βCuY2- = 1018.80 ; Y(H) = 107.25 (pH = 5)

β1,1 Cu(OH) =107.0; β1,2 Cu(OH)2 =1013.68; β1,3 Cu(OH)3 = 1017.0; β1,4 Cu(OH)4 = 1018.5

αCu(OH) = 1 +  βCu(OH)[OH]i = 1+107.10 – 9 +1013,68.(10 – 9)2

i 1

+1017. (10 – 9)3 + 1018.5 . (10 – 9)4 ≈ 1

1 1
 CuY '   CuY  10
18, 8
 1011, 55

 Cu( OH )Y ( H ) 1  107 , 25

Complexation reaction-Effect of complexation

EX: Calculate β’MgY at pH 11

Complexation reaction-Effect of complexation
Complexation reaction-Effect of precipitation
 If A is affected by Z1 to form A(Z1):

A + p D
+ + +
Z1 Z2 Z3
↓↑ TA(Z1) ↓↑ TP(Z2) ↓↑ TD(Z3)
A(Z1) p(Z2) D(Z3)
Combination of secondary and main equilibrium:
A(Z1) + p  D + Z1
[ D][ Z 1 ] [ A]
D'    D .TA( Z 1)
[ p] [ A]

Generally, when TA(Z1) << 1, Tp(Z2) << 1 và TD(Z3) << 1:

TA( Z 1) .T p ( Z 2 )
D' D .
TD ( Z 3 )
Complexation reaction-Effect of precipitation
EX: Calculate the conditional formation constant of Ag(CN)2
when adding 50 mL of 10-2M KI to 50 mL of Ag(CN)2
Precipitation reaction-Effect of Complexation
A + p D↓
+ +
Z1 Z2
αA(Z1)↓↑ αp (Z2) ↓↑
A(Z1)1,… p(Z2)1,…

o Main equilibrium: T = [A].[p]

o Combination of sec. and main equil.
 Conditional solubility product:
T ’ = [A’].[p’] = [A].[p].A(Z1). p(Z2)
 T’ = T .α A( Z1) . αp( Z2)
o If D is formed from reaction between nA and mp
T’ = T .αnA(Z1) . αmp (Z2)
Precipitation reaction-Effect of Complexation
EX: Calculate T’(CaF2) at pH 1
Precipitation reaction-Effect of Complexation
Effect of Complexation on A + p D D
solubility of precipitate +
np
↓↑
Generally, [Di ] = β1,i [A] [p]i: Dp, Dp2…Dpn
[D ] = Ap = β1,1[A] [p]1 = β1, 1Tst
[Dp1 ] = Ap2 = β1, 2 [A ] [p]2 = β1,2Tst [p]1
[Dpn-1 ] = Apn = β1,n [A ] [p] n = β1, n Tst [p ]n-1

Conditional solubility:
S’ = [A’] = [A] + [D] + [Dp1] +.. + [Dpn-1 ]

 1 n 1 
S '  T st    1 ,1   1 , 2 [ p ]   1 , 3 [ p ] ...   1 , n [ p ] 
1 2

 [ p] 
Precipitation reaction-Effect of Complexation
EX:
Calculate T’(AgCl) in water and in the solution with [Cl-] = 1 M
Precipitation reaction-Effect of Complexation
 Applications of conditional equilibrium
constants in Analytical Chemistry

 Calculation of concentrations of species at equilibrium

 Solubility of precipitates
 Effect of H+ on precipitation reaction
 Effect of redox reaction on precipitation reaction
 Calculation of pH of:
 Mixture of 2 weak acids and 2 weak bases
 Amphiprotic solutions
 Calculation of concentrations of species
at equilibrium
EX: Calculate concentration of species at equilibrium in a
solution of Cu2+ (10-2 M) and Y4- (2.10-2 M) at pH 5.

Cu2+ + Y4- CuY2-

+ +
OH- H+
αCu(OH)↓↑ α Y(H) ↓↑
Cu(OH)1,... HY3-,…

At pH=5 : αY(H) = 107.25

αCu(OH) = 1 +107.10-9 + 1013.68.10-18 + 1017.10-27 +1018.5.10-36 ≈ 1
1 1
 CuY '   CuY  10
18 .8
 1011 .55

 Cu (OH )Y ( H ) 1107.25

 Calculation of concentrations of species
at equilibrium
Cu2+ + Y4- CuY2-
[CuY 2 ] + +
CuY '   1011, 55

[Cu 2 ' ][Y 4 ' ] OH- H+

αCu(OH)↓↑ α Y(H) ↓↑
CY : initial concentration of Y4- Cu(OH)1,... HY3-,…
CCu: initial concentration of Cu2+
Mass conservation:
CCu = [CuY2-] + [Cu2+’]  [CuY2-] = 10- 2 M – [Cu2+’]
CY = [CuY2- ] + [Y4 –’]  [Y4 –’] = 10-2 M + [Cu2+’]
Replace [CuY2- ] and [Y4 –’] into βCuY’ with transformation, we have:
1011,55 [Cu2+’]2 + (1+ 109,55) [Cu2+’] – 10 – 2 = 0
 [Cu2+’] = 10 – 6,77 M

[CuY2-] = 10 –2 M – 10 –6.77 M ≈ 10 –2 M [Y4- ] 10 – 9,25 M

[Y4 –’] = 10 –2 M + 10 –6.77 M ≈ 10 –2 M
 Calculation of concentrations of species
at equilibrium
EX: Calculate concentrations of species at equilibrium in a
solution of [Mg2+] = 10-2 M and [Y4-] = 2x10-2 M at pH 11
Use of H+ for dissolving of precipitates
 Use of H+ for dissolving of precipitates

EX: Dissolve CdS in HNO3

Use of redox reactions for dissolving of precipitates
Use of redox reactions for dissolving of precipitates

EX: Dissolve CdS in HNO3

 pH calculation of a mixture of weak acid and
weak base
For acidic solution (pH<7): Mixture of HA and B-
[ H  ' ][ A ] [ H  ' ][ A ] kHA
k HA '  k HA . H ( B )   HA H+ + A –
[ HA] C HA
+
B–
Since [H+’] ≈ [A-] αH(B) ↓↑ kHB
[ H+’] = [H+]. αH( B) HB
[ H+’]2 = k’HA.CHA = kHA.CHA.αH( B)
[ H+ ]2.α2H(B) ≈ kHA.CHA.αH( B)
[ H+ ]2.α H(B) = kHA.CHA

 2 1 k HAC HA
[H ]   k HAC HA 
 H (B) 1   HB [ B  ]
 pH calculation of a mixture of weak acid and
weak base
For acidic solution (pH<7): Mixture of HA1, HA2 and A3-,A4-
 pH calculation of a mixture of weak acid and
weak base
For basic solution (pH>7): Mixture of B- and HA

kb
B - + H2O HB + OH –
+
HA
αOH( HA)↓↑ kA-
A–
+
H2O

 2 kbC B kbC B
[OH ]  
 OH ( HA) 1   A [ HA ]
 pH calculation of a mixture of weak acid and
weak base
For basic solution (pH>7): Mixture of A1-,A2- and HA3, HA4
 pH calculation of a mixture of weak acid and
weak base
EX: Calculate pH of a mixture of 10-2 M H2S, 2.10-3 M H2CO3
and NaOAc 10-2 M
 pH calculation of a mixture of weak acid and
weak base
EX: Calculate pH of a mixture of 10-2 M H2S, 2.10-3 M H2CO3
and NaOAc 10-2 M
 pH calculation of amphiprotic solution

Weak acid: HA- H+ + A2-

Amphiprotic spieces, HA-
Weak base: HA- + H+ H2A

Case 1: Acidity of HA- is stronger than its basicity

k2
 2 k 2C HA k 2C HA k 2C HA HA- ⇄ H+ + A2 –
[H ]    +
 H ( HA ) 1   H 2 AC HA 1  C HA HA –
k1 αH( HA) ↓↑k1
H2A
If CHA- / k1 >> 1:
 [H+]2 = k1.k2 or pH = ½(pk1 + pk2)

(pH < 7 k1.k2 > 10-14)

 pH calculation of amphiprotic solution

Case 2: Basicity of HA- is stronger than its acidity

 2 k b 2C HA k b 2C HA kb2

[OH ]  
 OH ( HA ) 1   A2 C HA HA - + H2O ⇄ HB + OH –
+
k b 2C HA
 HA-
C HA
1 αOH( HA)↓↑kb1
k b1
A 2–
+
If CHA / kb1 >> 1:
H2O
 [OH - ]2 = kb1 . kb2
 pOH = ½ (pkb1 + pkb2)
or pH = ½ (pk1 + pk2)
(pH > 7 k1.k2 < 10-14)
 pH calculation of amphiprotic solution

EX: Using formula to calculate pH of the following solutions:

a) NH4F(aq) 0.1M; b) NH4CN(aq) 0.01 M; c) NaHCO3(aq) 0.1 M

a) NH4F(aq) 0.1 M:
NH4F(aq) 0.1 M contains weak acid - NH4+ (kNH4+ = k2 = 10–
9.24 ) and weak base - F– (k = k = 10 –3.17)
HF 1
Since k1.k2 = 10 – 3.17 .10 – 9.24 > 10 –14
 Solution is acidic:
pH = ½ (pk1 + pk2) = ½ ( 3.17 + 9.24) = 6.21
 pH calculation of amphiprotic solution
b) NH4CN(aq) 0.01 M:
• Solution contains weak acid - NH4+ (kNH4+=k2= 10 – 9.24 )
and weak base - CN- (kHCN = k1 = 10 – 9.21)
• Since k1.k2 = 10 – 9,21 .10 – 9,24 < 10 – 14
 Solution is alkaline:
pH = ½ (pk1 + pk2) = ½ ( 9.21 + 9.24) = 9.23
c) NaHCO3(aq) 0,1 M:
NaHCO3(aq) → Na+(aq) + HCO3–(aq)
• pH of solution is decided by HCO3–(aq) which is an
amphiprotic species
• H2CO3 : k1 = 10-6.35; k2 = 10-10.32  k1.k2 < 10 – 14
 Solution is alkaline:
pH = ½ (pk1 + pk2) = ½ (6.35 + 10.32) = 8.33