Equilibrium Constants in Chemical Reactions
Equilibrium Constants in Chemical Reactions
AC1 1
Equilibrium constant of Reaction
(1)
a A+b B ←
→ cC +d D
(2)
Equilibrium constant
[C ] × [ D]
c d
K=
[ A] × [ B ]
a b
AC1 2
Equilibrium constants
AC1 3
Redox reactions
Electron-transfer reaction
Oxidation is a loss of electrons
Reduction is a gain of electrons
Reducing agent donates electron(s)
Oxidizing agent accepts electron(s)
AC1 4
Redox reaction - Example
Half-equation
− + 2+
MnO4 + 5e + 8 H
→ Mn
←
+ 4 H 2O
Fe 2+ − 1e ←
→
Fe 3+
Equation 0
EMnO − / Mn 2+ = 1.51V > EFe3+ / Fe 2+ = 0.77V
0
4
− 2+ + 2+ 3+
MnO4 + 5Fe + 8H ←
→ Mn
K
+ 5Fe + 4 H 2O
AC1 5
Half-equation
ox + ne kh
+
ox + mH + ne kh + m / 2 H 2O
+
ox + mH + ne pkh + m / 2 H 2O
Example
Cu 2+ / Cu , Cl 2 / 2Cl −
MnO4− / Mn 2+
Cr2O72− / 2Cr 3+
AC1 6
Redox reaction
Equilibrium constant of the reaction
+ n2 m
n2 ox1 + n1kh2 + n2 mH
←
→ n2 kh1 + n1ox 2 +
K (1)
H 2O
K(2) 2
n2 n1
[kh1 ] [ox ]
K (1) = n2 n1
2
+ n2 m
[ox1 ] [kh2 ] [ H ]
AC1 7
Redox reaction
Nernst equation – An equation relating
electrochemical potential to the concentrations of
products and reactants
+ m
RT [ ox ][ H ] RT [ox]
E=E +
0
ln or E=E +
0
ln
nF [kh] nF [kh]
+ m
0, 059 [ ox ][ H ] 0.059 [ox]
E=E +
0
lg or E=E + 0
lg
n [kh] n [kh]
R = 8.3144 J / mol 0 K , T = 298.160 K , F = 96493Cb / mol
E0 : standard potentials
n : number of electrons exchanged
AC1 8
Example
Half-equation
MnO4− + 5e + 8 H + ←
→
Mn 2+
+ 4 H 2O
Fe 2+ − 1e ←
→
Fe 3+
AC1 9
Redox equation ox1 / kh1 , ox2 / kh2
Half-equation
+ m
ox1 + mH + n1e ← → kh1 + H 2O
2
ox 2 + n2 e←
→ kh2
Potentials
+ m
0.059 [ox1 ][ H ]
E1 = E +
0
1 lg
n1 [kh1 ]
0.059 [ox2 ]
E2 = E2 +
0
lg
n2 [kh2 ]
AC1 10
Equilibrium
At equilibrium:
E1 = E2 = Eeq
+ m
0.059 [ox1 ][ H ] 0.059 [ox2 ]
⇒E + 0
1 lg = E2 +
0
lg
n1 [kh1 ] n2 [kh2 ]
n1
[ox2 ] [kh1 ] n2
n1n2 ( E − E )
0 0
lg n1 n2 + n2 m
= 1 2
[kh2 ] [ox1 ] [ H ] 0.059
n1n2 ( E10 − E20 )
n1n2 ( E − E )
0 0
lg K = 1
hay K = 10
2 0.059
0.059
AC1 11
Potential at equivalence
Case 1: + m
0. 059 [ ox ][ H ]
n1[ox1 ] = n2 [kh2 ] E1 = E1 +
0
lg 1
n1 [kh1 ]
n1[kh1 ] = n2 [ox2 ]
0.059 [ox2 ]
Eeq = E1 = E2 E2 = E +0
2 lg
n2 [kh2 ]
[ox1 ][ox 2 ]
⇒ =1
[kh1 ][kh2 ]
[ox1 ][ox2 ] + m
(n1 + n2 ) Eeq = n1 E + n2 E + 0.059 lg
0
1
0
2 [H ]
[kh1 ][kh2 ]
n1 E10 + n2 E20 0.059
⇒ Eeq = + lg[ H + ]m
n1 + n2 n1 + n2
AC1 12
Potential at equivalence
Case 2
+ m
ox1 + mH + n1e ← → pkh1 + H 2O , E1
0
2
ox 2 + n2 e←
→ kh2 , E 20
E10 > E 20
+ n2 m
n2 ox1 + n1kh2 + n2 mH ←
→
K
n2 pkh1 + n1ox 2 + H 2 O
2
AC1 13
Potential at equivalence
Case 2
n1[ox1 ] = n2 [kh2 ]
(1− p )
n1 [ ox ][ ox ] [ ox ][ kh ] [ kh ]
[kh1 ] = n2 [ox2 ] ⇒ 1
p
2
= 1
p
1
= 1
p [kh1 ] [kh2 ] [kh1 ] [ox1 ] p p
Eeq = E1 = E2
[ox1 ][ox2 ] + m
(n1 + n2 ) Eeq = n1 E + n2 E + 0.059 lg
0
1
0
2 p
[ H ]
[kh1 ] [kh2 ]
+ m
n1 E + n2 E
0 0
0.059 [ H ]
⇒ Eeq = 1
+ 2
lg [kh1 ](1− p )
n1 + n2 n1 + n2 p
AC1 14
Example
Calculte the equilibrium constant and the equilibrium
potential of the reaction between MnO4- / Mn2+ and
Fe3+ / Fe2+ at pH = 0.
E 0
MnO4− / Mn 2+
= 1.51V , E 0
Fe 3+ / Fe 2+
= 0.77V
MnO4− + 5Fe 2+ + 8 H + ←
→
K
Mn 2+
+ 5 Fe 3+
+ 4 H 2O
n1n2 ( E10 −E20 ) 5×1(1.51− 0.77 )
K = 10 0.059
= 10 0.059
= 10 62.7
= 5 ×10 62
[ A]0
⇒ [ A]eq = n
1 + ∑ β1,i [ p ] i
í =1
α A(p) : conditional
β í ,i [ p] [ A]0
coefficient (factor) i
[ Di ] = n
1 + ∑ β1,i [ p] i
í =1
AC1 21
Concentrations at the equilibrium
[PO43-] = 10-1M, H3PO4 :
−2 −7 −12
K a1 = 10 , K a 2 = 10 , K a 3 = 10
+ β1,1 2−
H + PO43−
←→ HPO 4 , β 1,1 = β 1 = 1012
k3
+ 3− β1, 2 −
2 H + PO4 ← → H 2 PO4 , β1, 2 = β1.β 2 = 10 19
k2,3
+ 3− β1,3
3 H + PO4 ← →
3 4 1,3
H PO , β = β . β
1 2 3. β = 10 21
k1,3
[ HPO ] 2− [ H 2 PO4− ]
β1, 2 =
β1,1 = + 1 4
3− [ H + ]2 [ PO43− ]eq
[ H ] [ PO ] 4 eq [ H 3 PO4 ]
β1,3 =
[ H + ]3 [ PO43− ]eq
AC1 22
Concentrations at the equilibrium
[ H + ] = [OH ]− = 10 −7 M [ A]0
[ A]eq = n
1 + ∑ β1,i [ p ] i
−1 í =1
10
[ PO43− ]cb =
1 + 1012 [ H + ] + 1019 [ H + ]2 + 10 21[ H + ]3
= 0,5 ×10 −6 = 5 ×10 −7 M
[ HPO42 − ] = β1,1[ H + ]1[ PO43− ]eq
= 1012 × (10 − 7 ) × 5 × 10 − 7 = 5 × 10 − 2 M
[ H 2 PO ] = β1, 2 [ H ] [ PO ] = 5 ×10 M
−
4
+ 2 3−
4 eq
−2
[ D] 1 1 1
βD = n
, β D↓ = , ⇒ β D × β D↓ = n
=
[ A][ p] [ D] [ A][ p] Tst
Solubility product constant (Ksp = Tst)
The equilibrium constant for a reaction in
[ A][ p] = Tst
n
which a solid dissociates into its ions (Ksp)
Solubility
S = [ D] + [ A] ≈ [ A]
AC1 24
Prepicitation Reaction
Example 1
Ag + + Cl −
→
AgCl ↓
←
s s s
+ − −9.75
TAgCl = [ Ag ][Cl ] = s × s = 10
−5
or=
s 1.3 × 10 M
AC1 25
Precipitation Reaction
Example 2
2 Ag + + CrO42−
→ Ag 2CrO4 ↓
←
2s s s
+ 2 2−
K sp = TAg 2CrO4 = [ Ag ] [CrO ]
4
−11.95
= (2 s ) × s = 4 s = 10
2 3
−5
or s ≈ 2.5 ×10 M
AC1 26
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
AC1 27
Dissociation constant of acid
HCl → Cl − + H + → OH − + H +
H 2O ←
→ CH 3COO − + H +
CH 3COOH
KA
A − + H 2O ←
→ HA + OH −
[ HA][OH − ] [ H + ] 10 −14
KB = K = × + =
A− −
[A ] [ H ] K HA
AC1 29
Dissociation constant for
acids and bases
−14
10
CH 3COOH ( K HA = 10 − 4.75 ) ⇒ K CH COO − = − 4.75 = 10 −9.25
3
10
−14
10
NH 4OH ( K B = 10 − 4.76 ) ⇒ K NH + / NH = − 4.76 = 10 −9.24
4 3
10
k > 100 : strong acid
10-3 < k < 100: medium acid
10-10 < k < 10-3: weak acid
k < 10-10: very weak acid
AC1 30
pH of an acid or base
Acid (monoprotic acid)
Strong acid Medium acid
Weak acid Polyprotic acid
Base (monoprotic base)
Strong base Medium base
Weak base Polyprotic base
Salt
Buffer
AC1 31
Strong acid
pH = -lg [H+]
AC1 32
Medium acid
[ H + ][ A− ] [ H + ]2 [ H + ]2 [ H + ]2
k HA = = = =
[ HA] [ HA] C HA − [ A ] C HA − [ H + ]
−
+ 2 +
⇒ [ H ] + k HA [ H ] − k HAC HA = 0
AC1 33
Weak acid
+ −
HA →
← H +A
+ − 10–2 M CH3COOH (pKa =
[H ] = [ A ]
4,76) (pH = 3.39)
[ HA] ≈ C HA
+ − + 2 + 2
[ H ][ A ] [ H ] [ H ]
k HA = = =
[ HA] [ HA] C HA
+
⇒ [ H ] = k HAC HA
AC1 34
Polyprotic acid k1 >> k 2 ≈ 10 4
+ −
A → H
H2 ←
k1
+ HA + −
− + 2−
HA1 ←→ H
k1
+ A1
HA
←→ H + A
k2
+ −
HA2
←→
k2
H + A2
AC1 35
Polyprotic acid k1 ≈ k 2
HA1←
+ −
k HA1
→ H + A1
HA2 ←
+ −
k HA2
→ H + A2
AC1 36
Polyprotic acid k1 ≈ k 2
n
or [ H ] = ∑ k HAi C HAi
+ 2
i =1
AC1 37
Polyprotic acid - Example k1 ≈ k 2
n
[ H ] = ∑ k HAi C HAi = 10
+ 2 −3.70 −2
×10 + 10 − 4.60
×10 −2
i =1
AC1 38
Strong base
10–2 M NaOH (pH = 12)
k − −14
A + H 2O ←
−
→ HA + OH − 10
=
A
k
−14
A− k HA
− 10
[OH ] = C − ⇒ +
=C −
A [H ] A
⇒ pH = 14 + lg C −
A
Khi C −8
≈ 10 − 10 −7
M H 2O → H + + OH −
A−
−14
− + + 10
[OH ] = [ BH ] + [ H ] H 2O = C +
A− [OH − ]
⇒ [OH − ]2 − C − [OH −
] − 10 −14
=0
A
AC1 39
Medium base
−14
10
A − + H 2O ←
k −
→ HA + OH − k =
A−
A
k HA
[ HA][OH − ] [OH − ]2 [OH − ]2
k = = =
A− −
[A ] −
[A ] C − − [OH ]−
A
⇒ [OH − ]2 + k − [OH −
] − k −C =0
A A A−
AC1 40
Weak base
10–2 M NH4OH (pK A- = 4.76) (pH = 10.61)
k −
A + H 2O ←
−
→ HA + OH
A −
C − ≈ [ A− ]
A
[ HA] = [OH − ]
[ HA][OH − ] [OH − ]2 [OH − ]2
k = = =
A− −
[A ] −
[A ] C −
A
−
⇒ [OH ] = k − C
A A−
AC1 41
Polyprotic base k n << k n−1 ≈ 10 4
2− − − − −
A + H 2O←
→ HA + OH
A1 + H 2O←
→ HA1 + OH
k2 k1
−
HA + H 2O←
→ H 2 A + OH
− A2− + H 2O←
→
HA2 + OH −
k1 k2
pH of monoprotic base
AC1 42
Polyprotic base - Example
10–2 M Na2CO
k n << k n−1 ≈ 10 4
3
CO3 2− + H 2O ←
→
HCO3
−
+ OH −
− −
HCO3 + H 2O←
→
H 2 CO3 + OH
AC1 43
Polyprotic base k1 ≈ k 2
k −
−
A1 + H 2O←
→ HA1
A1
+ OH −
k −
− −
A2 + H 2O ←
→ HA2
A2
+ OH
− −
[ HA1 ][OH ] [ HA1 ] + [ A1 ] = C − (3)
k = (1) A1
A1− −
[ A1 ]
[ HA2 ] + [ A2− ] = C − ( 4)
[ HA2 ][OH − ] A2
k = ( 2)
A2− −
[ A2 ] [OH − ] = [ HA1 ] + [ HA2 ](5)
AC1 44
Polyprotic base k1 ≈ k 2
− −
− [kA1 ] k − [ A2 ]
− A A
[OH ] = 1
+ 2
[OH − ] [OH − ]
⇒ [OH − ] = k − [ A −
1 ]+ k − [ A −
2]
A1 A
2
[ A1− ] ≈ C − , [ A −
2]≈C
A1 A2−
⇒ [OH − ]2 = k − C + k −C
A1 A1− A2 A2−
n
− 2
[OH ] = ∑ k − C −
A A i =1 i i
AC1 45
Salts
Strong acid and strong base
HCl + NaOH NaCl + H2O (1) pH = 7
Neutral ions (Cl-, Br-, I-, NO3- ; Na+, K+, Li+, Ca2+,
Mg 2+, Ba2+)
Acidic ions (HSO4-, H2PO4- ; H+, Al3+, NH4+, Zn2+ ,
Cu2+, …)
Basic ions (OH-, HS-, CO32-, HCO3-, PO43-, HPO42-,
S2-, CN-, CH3COO-)
AC1 47
pH of a buffer
AC1 48
pH of a buffer
solution
+ −
HA
←
k HA
→ H + A
pH (HA và MA)
→
MA ←
M +
+ A −
−
[ HA] + [ A ] = C A + C B (2) A − + H 2O
→
←
HA + OH −
[ H + ] + [ M + ] = [OH − ] + [ A− ] [ HA]
+
[ H ] = k HA − (1)
hay [ H + ] + C B = [OH − ] + [ A− ] [A ]
− + −
⇒ [ A ] = C B + [ H ] − [OH ](3) CA
+
[ H ] ≈ k HA
⇒ [ HA] = C A − [ H + ] + [OH − ](4) CB
+ −
+ C − [ H ] + [OH ] CB
⇒ [ H ] = k HA A
+ − pH = pk HA + lg
C B + [ H ] − [OH ] C A
AC1 49
pH of a buffer
solution
Henderson–Hasselbalch equation
Equation showing the relationship
between a buffer’s pH and the relative
amounts of the buffer’s conjugate weak
acid and weak base.
AC1 50
pH of a buffer solution
pH (HA và MA) – Example
CB
pH = pk HA + lg
CA
−2
10
= 4.76 + lg − 2 = 4.76
10
AC1 51
pH of a buffer solution - Example
pH (HA và MA) – Example
CB
pH = pk HA + lg
CA
1) Calculate pH of a mixture of 10–2 M CH3COOH and 10–2 M
CH3COONa
2) Calculate pH of a mixture of 250 mL of 10–2 M CH3COOH
and 100 mL of 10–2 M CH3COONa.
3) Calculate pH of the solution (2) after adding 2 mL of 10–2
M NaOH or 2 mL of 10–2 M HCl
AC1 52
pH of buffer - Example
CB
pH = pk HA + lg
CA
1) Mixture of 10–2 M CH3COOH and 10–2 M CH3COONa
10 −2
pH = 4.76 + lg − 2 = 4.76
10
2) Calculate pH of a mixture of 250 mL of 10–2 M CH3COOH
và 100 mL of 10–2 M CH3COONa.
3
10
10 − 2 ×10 −3 ×100 ×
pH = 4.76 + lg 350 = 4.36
3
10
10 − 2 ×10 −3 × 250 ×
350
AC1 53
pH of a buffer solution
3) Calculate pH of the solution (2) after adding 2 mL dd
NaOH 10–2 M or 2 mL HCl 10–2 M.
−2 −3 103 −2 −3 103
10 ×10 ×100 × + 10 ×10 × 2 ×
pH = 4.76 + lg 350 350 = 4.37
3 3
10 10
10 − 2 ×10 −3 × 250 × − 10 − 2 ×10 −3 × 2 ×
350 350
4) How many grams (m) of CH3COONa is needed to add to
the solution (2) to have a solution with pH =5?
3
10
10 − 2 ×10 −3 ×100 × +x
pH = 4.76 + lg 350 =5
3
10
10 − 2 ×10 −3 × 250 ×
350 −3
m= x ×10 × 350 × 82
AC1 54
pH of a buffer solution
pH (B và BH+)
BH +
←→
ka
B + H + NH3 and NH4Cl
+ −
B + H 2O ←
→ BH + OH
kb
+
[ B ][ H ] k w
ka = +
=
[ BH ] kb CB
or pH = pk a + lg
+ CA
+ [ BH ]
[ H ] = ka
[ B]
+
+ [ BH ]
− log[ H ] = − log ka − log
[ B]
AC1 55