Chapter 2

EQUILIBRIUM CONSTANT
OF REACTION
 CONTENT

Equilibrium constants in:

 Chemical reactions (redox, acid-base,
complexometric and precipitation reactions)
 Stepwise or overall equilibrium constants
 Acid-base dissociation constants
 Formation constants
 Solubility product constants
 REDOX REACTION
Electron-transfer reaction

Ox1 + Red2  Red + Ox
(1)
( 2)1 2
 Oxidation is a loss of electrons
 Reduction is a gain of electrons
 Reducing agent donates electron(s)
 Oxidizing agent accepts electron(s)
“OIL RIG” is a good mnemonic

4
 REDOX REACTION
 HALF-REACTION
The potentials are for the half-reaction written as a reduction
 reduction potentials (electrode potential)
aOx + ne-  bRed
 Nerst equation for reduction potential:
a
RT [Ox ]
E  Eo  ln (3.1)
nF [Re d ]b
E is the reduction potential at the specific concentrations;
R is gas constant, F is Faraday constant, n is nr of
electrons exchanged, [Ox] and [Red] are molarity of oxidizing
and reducing agent respectively.
 REDOX REACTION
 HALF-REACTION
 Replace R = 8.314 J/mol.K; T = 298.16 K, F = 96493 C/mol,
convert ln to lg:
0.059 [Ox]
EE  o
lg (3.2)
n [Re d ]
When [Ox] = [Red] = 1M => E = E0.
 E0: standard electrode potential
Standard conditions: [aqueous solution] = 1 M; Pgas = 1
atm, pure solid & liquid, temperature is often considered
as 25oC
 !! For pure solid and liquid: [solid/liquid] = 1 M
 REDOX REACTION
Example:
A solution is 10−3 M in Cr2O72− and 10−2 M in Cr3+. If the pH is
2.0, what is the potential of the half-reaction at 298K?
Solution

8
 REDOX REACTION


9
 REDOX REACTION
 Mixing (Ox1/Kh1) and (Ox2/Kh2)  REDOX reaction
n2Ox1 + n1Kh2 

(1)
n1Ox2 + n2Kh1 (1)
( 2)

Equilibrium constant K(1):

[Ox2 ]n1 [ Kh1 ]n2
K (1)  n2 n1
[Ox1 ] [ Kh2 ]

 At equilibrium: E1 = E2 ; by writing and transforming

Nerst quations of 2 half-equations, we have:
n1n2 ( E1o  E 2o )

K (1)  10 0 , 059
 REDOX REACTION
 Nerst equation for redox reaction:

n2Ox1 + n1Kh2 


(1)
n1Ox2 + n2Kh1
( 2)

n1 n2
0.059 [Ox ] [ Kh ]
E  Eo  lg 2 1
n1n2 [Ox1 ]n2 [ Kh2 ]n1
 Example

A 5.0mL portion of 0.10 M Ce4+ solution is added to 5.0mL of 0.30

M Fe2+ solution. Calculate the potential at 298K of a platinum
electrode dipping in the solution (relative to the NHE).
 Q&A
1. Calculate (a) the standard potential, (b) the equilibrium
constant, and (c) the potential when [Ag+]=0.020 M and
[Cd2+]= 0.050 M, for the following reaction at 25oC.

2. For the following reaction at 25oC

calculate (a) the standard potential, (b) the equilibrium

constant, and (c) the potential under these conditions:
[Fe2+]= 0.50 M, [Fe3+]= 0.10 M, [MnO4-]= 0.025 M,
[Mn2+]= 0.015 M, and a pH of 7.00.
 REDOX REACTION
Equivalence point potential
n2Ox1 + n1Kh2  n1Ox2 + n2Kh1 E1o  E 2o

 Equivalence point: equivalent quantities of reactants

have been mixed
n1[Ox1 ]  n2 [ Kh2 ] [Ox1 ] n2 [Ox2 ] n1
  and 
n1[ Kh1 ]  n2 [Ox2 ] [ Kh2 ] n1 [ Kh1 ] n2
 REDOX REACTION
Equivalence point potential
 Equivalence point potential
At equilibrium: E1 = E2 = Eeq
0,059 [Ox1 ] [Ox1 ]
Eeq E 0
1 lg or n1 Eeq  n1 E1  0,059 lg
0
n1 [Re d1 ] [Re d1 ]
0,059 [Ox2 ] [Ox2 ]
Eeq E 0
2 lg or n2 Eeq  n2 E2  0,059 lg
0

n2 [Re d 2 ] [Re d 2 ]
n1 E1o  n2 E 2o 0,059 [Ox1 ] [Ox2 ]
 Eeq = + lg 
n1  n2 n1  n2 [Re d1 ] [Re d 2 ]
[Ox1 ] [Ox2 ] n2 n1
since, lg  = lg  = lg1 = 0
[Re d 2 ] [Re d1 ] n1 n2
n1 E1o  n2 E 2o
so, Eeq =
n1  n2
 REDOX REACTION
Equivalence point potential
 Equivalence point potential
** Presence of H+ in half-reaction of Ox1/Kh1:
n2Ox1 + n1Kh2 + n2mH+ 

(1)
n1Ox2 + n2Kh1 + ½n2mH2O
( 2)

n1 E1o  n2 E 2o 0,059
Eeq = + lg[ H  ]m
n1  n2 n1  n2
*** Presence of H+ and different stoichiometric coefficients of Ox1
and Red1 :

n2Ox1 + n1Red2 + n2mH+ 

(1)
n1Ox2 + n2pRed1 + ½n2mH2O
( 2)

n1[Ox1 ]  n2 [Re d 2 ]  [Ox1 ] n2 [Ox2 ] n1

  và 
n1[Re d1 ]  n2 p[Ox2 ] [Re d 2 ] n1 [Re d1 ] n2 p
n E n E
o o
0,059   m [Re d1 ]
1 p

Eeq = 1 1 2 2
+ lg  [ H ] 
n1  n2 n1  n2  p 
 Q&A

1. One beaker contains a solution of 0.0200 M KMnO4, 0.00500 M

MnSO4, and 0.500 M H2SO4; and a second beaker contains 0.150 M
FeSO4 and 0.00150 M Fe2(SO4)3. The two beakers are connected by
a salt bridge, and platinum electrodes are placed in each. The
electrodes are connected via a wire with a voltmeter in between.
What would be the potential of each half-cell (a) before reaction and
(b) after reaction? What would be the measured cell voltage (c) at the
start of the reaction and (d) after the reaction reaches equilibrium?
Assume H2SO4 to be completely ionized and in equal volumes in
each beaker.
 Q&A

2. Calculate KC and the potential at the equivalence point

when 100 ml of 0.1 N K2Cr2O7 is mixed with 100 ml of 0.1N
FeSO4 at pH 0. (Determine equivalent weight of reactants)
 Dissociation and formation
constants – stepwise constants
A + p 
(1)
 D
( 2)

where A (acceptor), D (donor), p: exchanged species

[ D]:  (K ): formation constant

K (1)    f
[ A][ p]

[ A][ p]
K ( 2)  k  k = 1/: dissociation constant
[ D]
 Dissociation and formation
constants – stepwise constants
 Stepwise constants
β1
A + p ⇄ D1 1 
[ D1 ]

1
kn
[ A][ p] k n
β2
D1 + p ⇄ D2 [ D2 ] 1
Kn-1 2  
[ D1 ][ p] k n 1
βn  [D1] = β1 [ A ] [ p ]
Dn-1 + p ⇄ Dn
k1 [D2 ] = β2 [ D1 ] [ p ] = β1 . β2 [ A ] [ p ]2

Generally, at “i” step:

Di - 1 + p ⇄ Di

[ Di ] 1 [Di ] = β1.β2 ….βi [ A ] [ p ]i

 i   
[ Di 1 ][ p] k i ' ( where i + i’ = n + 1)
 Dissociation and formation
constants – overall constants
Consider a 2-steps equilibrium:
β1,2
A + 2p  
 D2
k1,2
[ D2 ] 1
 Overall formation constant:  1, 2  2

[ A][ p] k1, 2

 Relationship between overall and stepwise constants:

 Generally, for n-steps equilibrium:

1 [Di ] = β1, i[A][p]i
1,i  1 . 2 .... i 
k n .k n 1 ...k i ' where i + i’ = n + 1
CONCENTRATION AT EQUILIBRIUM
Consider general case:
A + p 


 D1 + p 


 D2 + p ….. 


 Dn
CA or [A]o: initial concentration of A
??? Calculation of [A] and [Di] at equilibrium
Mass Balance: [A]o = [A]+[D1]+[D2]+ …+ [Dn]
Knowing [Di] =  1,i [A].[p]i
 [A]o = [A] +  1,1 [A].[p]1 +…+ 1,n [A].[p]n
OR n where A[p]:
[ A]o  [ A].{1   1,i [ p ] }  [ A]. A[ p ]
i
conditional
i 1 coefficient

[ A]o [ A]o 1,i [ p ]i

[ A]  [ D ]i 
 A[ p ]  A[ p ]
 CONCENTRATION AT EQUILIBRIUM
Example 1: Establish expression for Y[H+] of EDTA (H4Y) and
equilibrium concentration of all species, knowing k1 = 10-1,99, k2
= 10-2,67, k3 = 10-6,27, k4 = 10-10,95
( ) ( )
Y4- + H+ 
  
1  HY3-
  HY3- + 
H+  
2
 H2Y2-
(k ) (k )
4 3

( ) ( )

 3 
  4
H2Y2- + +
H  
(k )
 H3Y- H3Y- + H+  
(k )
 H4Y
2 1

β1,1 = β1 = 1/k4 = 10 10,95 β1,2 = 1/ k3.k4 = 1017,22

β1,3 = 1/k2.k3.k4 = 10 19,89 β1,4 = 1/ k1. k2. k3.k4 = 10 21,89

α Y(H+) = 1 + β1,1 [H+] + β1,2 [H+]2 + β1,3 [H+]3 + β1, 4 [H+]4

= 1 +1010,95 .[H+] + 1017,22.[H+]2 + 1019,89.[H+]3 + 10 21,89.[H+]4
CONCENTRATION AT EQUILIBRIUM
Equilibrium concentration of species:

[Y ]o [Y ]o1010 ,95 [ H  ]
[Y 4 ]  3
[ HY ] 
 Y(H  )  Y(H  )

2 [Y ]o1017 , 22 [ H  ]2 [Y ]o1019 ,89 [ H  ]3

[ H 2Y ]  [ H 3Y  ] 
 Y(H  )  Y(H  )

[Y ]o10 21,89 [ H  ]4
[ H 4Y ] 
 Y(H  )
 CONCENTRATION AT EQUILIBRIUM
Equilibrium concentration of species:

pH 1 2 3 4

Y(H+) 1017,93 1014,24 1011,4 109,24

pH 5 6 7 8

Y(H+) 107,24 105,41 104,02 102,96

pH 9 10 11 12

Y(H+) 101,96 101,0 100,28 100,04

 CONCENTRATION AT EQUILIBRIUM
Problem 1: Calculation of concentration of all species
present at equilibrium of 0.1 M PO43-(aq), pH = 1
( )
PO43- + 
H+  

1
 HPO42-
(k )
3

( )
 
2 
HPO42- + H+  
(k ) H2PO4-
2

( )
3
H2PO4- + H+ 

(k )
 H3PO4
1

Knowing that k1 = 10-2.12; k2 = 10-7.21; k3 = 10-12.38

 PRECIPITATION REACTION
 

A + np  D 
D

 D
D


[ D] 1
 Formation constant:
D   D 
1 [ A][ p]n [ D]
  D . D 
K sp

 Solubility (S): S = [D] + [A] (S  [A] as [D] ~ 0).

 If D ~ 0 : From given or Ksp  S

Given slightly soluble compound, AmBn:




AmBn mAn+ + nBm+ TAmBn
S mn
Ksp = [An+]m.[Bm]n  m m .n n
 PRECIPITATION REACTION
Example:
 PRECIPITATION REACTION
Example:
Calculate the solubility of Pb(IO3)2 in 1.0 × 10–4 M Pb(NO3)2
(2.3x10-5 mol/L)
 ACID-BASE REACTIONS
 Bronsted-Lowry theory (1923)
- acid is proton donor and base is proton acceptor
 Lewis theory (1923)
- acid is an electron pair acceptor and base is an
electron pair donor
- complexation reactions between metal ions and
ligands
 Amphiprotic - A species capable of acting as both an
acid and a base.
 Acid dissociation constant (Ka): The equilibrium
constant for a reaction in which an acid donates a
proton to the solvent
ACID/BASE DISSOCIATION CONSTANT

HA 


 H+ + A-
Acid dissociation constant, k HA:
 
[ H ][ A ]
k HA  ka 
[ HA]




A- + H2O HA + OH-
Base dissociation constant, k :
A

[ HA][OH ] k w
k A  kb  

[A ] k HA
 ACID/BASE DISSOCIATION CONSTANT
H2O 


 H+ + OH-
Ionic product of water, kw :
 
kw  [ H ][OH ]
For a conjugate acid-base pair: k HA .k A  kw
For aqueous solution: pH + pOH = pkw
At 25oC: kw = 10-14
At 25oC : pH + pOH = 14
***[acid] or [base] >10-7 => dissociation of H2O is negligible
EX: A 1.0 × 10−3 M solution of hydrochloric acid is
prepared. What is the hydroxide ion concentration?
ACID/BASE DISSOCIATION CONSTANT
 pH CALCULATION
 pH of an acid or base
 Monoprotic acid
Strong acid Medium acid Weak acid
 Polyprotic acid

 Monoprotic base
Strong base Medium base Weak base
 Polyprotic base

 pH of Salt (aq)
 pH of Buffer (aq)
 pH of monoprotic acid
For a monoprotic acid, HA, with initial concentration, CHA:
HA 
 H+

 + A-
H2O 
 H+

 + OH-

General equation of [H+] is a combination of:

[ H  ][ A ]
 Equilibrium constant of acid: k HA  (a)
[ HA]

 Mass conservation: [HA] + [A-] = CHA (b)

 Charge neutralization: [H+] = [OH-] + [A-] (c)

 Ionic product of water: [H+].[OH-] = kH2O (d)

 pH of monoprotic acid
strong acid
 








 pH of monoprotic acid
medium acid
HA 


 H+ + A-

[HA] + [A-] = CHA

[H+] = [A-]
 
[ H ][ A ]
k HA 
[ HA]
=> [H+]2 + kHA [H+]–kHACHA = 0

Example: pH of 10-2 M HIO3(aq) (pKa = 0.9)

 pH of monoprotic acid
weak acid


HA 
 H+ + A-

[HA] ~ CHA
[H+] = [A-]
[ H  ][ A ]
k HA 
[ HA]

=> pH= ½ pkHA – ½ lg CHA

Example: pH of 10-2 M CH3COOH(aq) (pKa = 3.39)

 pH of polyprotic acid/mixture of
monoprotic acids
A. Polyprotic acid or Mixture of monoprotic acid
[k1>>k2 (~104)]
H2A 


 H+ + HA-
HA- 


 H+ + A2-
HA1 


 H+ + A1-
HA2 


 H+ + A2-
=> pH of monoprotic acid (k1)
Example: calculate pH of 10-2 M H2CO3(aq) knowing
pKa1 = 6.35, pKa2= 10.32
 pH of polyprotic acid/mixture of
monoprotic acids
B. Polyprotic acid or Mixture of monoprotic acid
[k1 ~k2]

n
[ H ]   k HAi .C HAi
 2

i 1

Example: acid m-phthalic, 10-2 M C6H4(COOH)2(aq)

(pKa1 = 3.70, pKa2 = 4.60) (pH = 2.87)
 pH of monoprotic base
strong base
 








 pH of monoprotic base
medium base
B + H2O 


 BH+ + OH-
CB CB CB

[B] + [BH+] = CB
[BH+] = [OH-]

[ BH  ][OH  ]
kB 
[ B]
=> [OH-]2 + kB[OH-] – kBCB = 0
 pH of monoprotic base
weak base
B + H2O 


 BH+ + OH-
CB CB CB

[B] ~ CB
[BH+] = [OH-]

[ BH  ][OH  ]
kB 
[ B]
=>pH= 14 – ½ pkB + ½ lg CB

Example: pH of 10-2 M NH4OH(aq) (pkB = 4.76)

 pH of polyprotic base/mixture of
monoprotic bases
A. Polyprotic base or Mixture of monoprotic base
[k1>>k2 (~104)] => pH of monoprotic base (k1)
CO32- + H2O 


 HCO3- + OH-
HCO3- + H2O 


 H2CO3 + OH-
Example: calculate pH of 10-2 M Na2CO3(aq) knowing pKa1
= 6.35, pKa2= 10.32 (11.13)
B. Polyprotic acid or Mixture of monoprotic acid
n
[OH  ]2   k Bi .C Bi
[k1 ~k2)]

i 1
 pH of acid solution
Calculate the pH of a solution prepared by mixing 2.0mL of
a strong acid solution of pH 3.00 and 3.0mL of a strong
base of pH 10.00.
 Solution
[H+] of acid solution = 1.0 × 10−3 M
mmol H+ = 1.0 × 10−3 M × 2.0 mL = 2.0 × 10−3 mmol
pOH of base solution = 14.00 − 10.00 = 4.00
[OH−] = 1.0 × 10−4 M; mmol OH− = 1.0 × 10−4 M × 3.0 mL = 3.0 × 10−4 mmol
There is an excess of acid.
mmol H+ = 0.0020 − 0.0003 = 0.0017 mmol
Total Volume = (2.0 + 3.0) mL = 5.0 mL
[H+] = 0.0017 mmol/5.0 mL = 3.4 × 10−4 M
pH = −log 3.4 × 10−4 = 4 − 0.53 = 3.47
 pH of acid solution
Calculate the pH and pOH of a 1.0 × 10−7 M solution of
HCl.
 Solution
Equilibria: HCl → H+ + Cl− H2O → H+ + OH−
[H+][OH−] = 1.0 × 10−14
[H+]H2Odiss.= [OH−]H2Odiss.= x Since the hydrogen ions contributed from the ionization
of water are not negligible compared to the HCl added,
[H+] = CHCl + [H+]H2Odiss.
Then, ([H+]HCl + x)(x) = 1.0 × 10−14
(1.00 × 10−7 + x)(x) = 1.0 × 10−14
x2 + 1.00 × 10−7x − 1.0 × 10−14 = 0
X = 6.2 × 10−8M
Therefore, the total H+ concentration = (1.00 × 10−7 + 6.2 × 10−8) = 1.62 × 10−7 M:
pH = −log (1.62 × 10−7) = 7 − 0.21 = 6.79; pOH = 14.00 − 6.79 = 7.21
 Buffers - Keeping the pH Constant
(or Nearly So)

 Buffer solution
 a solution that resists change in pH when a small
amount of an acid or base is added or when the
solution is diluted.
 a mixture of a weak acid and its salt [acidic buffer]
or a weak base and its salt [basic buffer]
 C or CB
[ H ]  k HA A
pH  pk HA  lg
CB CA
(Henderson–Hasselbalch equation)
 buffering capacity of the solution
 Q&A
1. Calculate the pH of a buffer prepared by adding 10
mL of 0.10 M acetic acid to 20 mL of 0.10 M sodium
acetate (5.06).
2. Calculate the pH of a solution prepared by adding 25
mL of 0.10 M sodium hydroxide to 30 mL of 0.20 M
acetic acid (this would actually be a step in a typical
titration). (4.61)
3. Calculate the pH of the buffer when 3.00 mL of 1.00
M HCl is added to 100 mL of a buffer containing 0.100
M acetic acid and 0.0500 M sodium acetate.(3.95)
 pH of salt solution
 Salt from strong acid and strong base (NaCl)
 pH = 7 (25oC)
 Salt from strong acid and weak base
 weak acid
if [H+] << CHA
pH = ½ pkHA - ½ lgCsalt
 Salt from weak acid and strong base
 weak base
if [OH-] << CA-
pH = 14 - ½ pkA- + ½ lgCsalt
= 7 + ½ pkHA + ½ lgCsalt
 pH of salt solution

neutral Acidic Alkaline

OH–, HS–, CO32–
Cl– ,l – ,Br – ,
HCO3– PO43–,
Anion NO3– , ClO4– , SO42 HSO4–, H2PO4 –
– HPO42–, S2–
CN – ,CH3COO –

H +, Al 3+, NH4+,
Na +, K +, Li +,
Zn2+, Cu2+ and
Cation Ca 2+, Mg 2+, [Al(H2O)5(OH)]2+
other transition
Ba 2+
metal cations