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Equilibrium Constants in Chemical Reactions

The document discusses equilibrium constants for chemical reactions. It defines equilibrium constants and describes how they determine the relative concentrations of products and reactants at equilibrium. It also discusses different types of equilibrium constants, including for redox, acid-base, complexometric, and precipitation reactions. Redox reactions are electron transfer reactions that can be balanced and have an associated equilibrium constant.
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0% found this document useful (0 votes)
155 views55 pages

Equilibrium Constants in Chemical Reactions

The document discusses equilibrium constants for chemical reactions. It defines equilibrium constants and describes how they determine the relative concentrations of products and reactants at equilibrium. It also discusses different types of equilibrium constants, including for redox, acid-base, complexometric, and precipitation reactions. Redox reactions are electron transfer reactions that can be balanced and have an associated equilibrium constant.
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

Chapter 3

Equilibrium constant of reaction

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

The equilibrium constant determines the relative


concentrations of products and reactants.

AC1 2
Equilibrium constants

 Chemical reactions (redox, acid-base,


complexometric and precipitation reactions)
 Stepwise or overall equilibrium constants
 Acid-base dissociation constants
 Formation constants
 Solubility product 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

 How to balance redox reactions (electron exchange,


charge of ions, elements)
E0: standard reduction electrode potentials

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+

 Potentials - Nernst equation


− + 8
− 2+ 0 . 059 [ MnO ][ H ]
E ( MnO4 / Mn ) = 1.51 + lg 4
5 [ Mn 2+ ]
3+
3+ 2+ 0 . 059 [ Fe ]
E ( Fe / Fe ) = 0.77 + lg
1 [ Fe 2+ ]

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

n1 E10 + n2 E20 0.059


Eeq = + lg[ H + ]m
n1 + n2 n1 + n2
5 ×1.51 + 0.77 0.059
= + lg(1)8 = 1.39V
5 +1 5 +1
AC1 15
Dissociation constants for acids
 [PO43-] = 10-1M, H3PO4 : stepwise
dissociation constants
K a1 = 10 −2 , K a 2 = 10 −7 , K a 3 = 10 −12
1
H 3 PO4 ←
→
k1
H+ + H 2 PO4− , β 3
= = 10 2
β3 k1
− + 2− 1
H 2 PO4 ← → H + HPO4 , β 2 =
k2
= 10 7
β2 k2
2− + 3− 1
HPO4 ←  →

k3
β1
H + PO4 , β 1 = = 10 12
k3
[ HPO42− ] [ H 2 PO4− ] [ H 3 PO4 ]
β1 = + 1 β2 = + 1 β3 = + 1
[ H ] [ PO43− ]cb [ H ] [ HPO4 ] 2−
[ H ] [ HPO42− ]
AC1 16
Formation constants for acids
+ β1,1 2−
H + PO43− 
←→ HPO 4 , β 1,1 = β 1 = 1012
k3
+ 3− β1, 2 −
2 H + PO4 ← → H 2 PO4 , β 1, 2 = β .
1 2β = 1019
k2,3
+ 3− β1,3
3 H + PO4 ←
  → H 3 PO4 , β1,3 = β1.β 2 .β 3 = 10 21
k1,3
2−
[ HPO ]
β1,1 = + 1 4
3−
[ H ] [ PO ] [ H 3 PO4 ]

4 eq
β1,3 = + 3 3−
[ H 2 PO ] [ H ] [ PO4 ]eq
β1, 2 = + 2
4
3−
[ H ] [ PO ]4 eq
AC1 17
Dissociation and formation
constants – stepwise
β1 constants
A + p k D1
n
β2 [ Di ]
D1 + p k D2 βi =
n −1 [ Di −1 ][ p]
− − − − − − − −
[ Di −1 ][ p]
βi ki ' =
β Di −1 + p k Di [ Di ]
A + np k D i'
[ Di ]
− − − − − − − −
β1,i =
β n −1 [ A][ p]i
Dn−2 + p k2
Dn−1
i
[ A][ p] 1
Dn−1 + p k Dn βn k1,i = =
1 [ Di ] β1,i
AC1 i + i' = n +1 18
Dissociation and formation
constants – Overall
β
constants
A + p k1,1 D1
1,1
β1, 2
A+2p k D2 1
1, 2 β1,1 = β1 =
kn
− − − − − − − − − − − − −

β1,i β1,i = β1.β 2 .β i


β A + ip k Di
A + np k D 1, i 1
βi =
− − − − − − − − − − − − −
ki '
β1,n −1
A + (n − 1) p k Dn−1
1, n −1
β1, n
A + np k Dn
1, n
AC1 19
Concentrations at the equilibrium
[ A]0 = C A = [ A]eq + [ D1 ] + [ D2 ] + ... + [ Di ] + ...[ Dn ]
[ Di ] = β1,i [ p ]i [ A]eq
[ A]0 = C A
= [ A]eq + β1,1[ p][ A]eq + β1, 2 [ p] [ A]eq + ...
2

+ β1,i [ p]i [ A]eq + ... + β1,n [ p ]n [ A]eq


[ A]0 = C A = [ A]eq {1 + β1,1[ p ] + β1, 2 [ p ]2 + ...
+ β1,i [ p ] + ... + β1,n [ p ] }
i n
α A(p) : conditional coefficient
n (factor)
[ A]0 = C A = [ A]eq {1 + ∑ β1,i [ p ]i } = [ A]eq α A( p )
i =1
AC1 20
Concentrations at the equilibrium

[ 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

[ H 3 PO4 ] = β1,3 [ H + ]3 [ PO43− ]eq = 5 ×10 −7 M


AC1 23
Precipitation reaction
βD βD↓
 ←
A + np ←
→
 D 
→ D ↓
 Formation constant

[ 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

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

AC1 27
Dissociation constant of acid
HCl → Cl − + H + → OH − + H +
H 2O ←

→ CH 3COO − + H +
CH 3COOH 
KA

Acid Conjugated base


[ H + ][CH 3COO − ]
K CH 3COOH = K =
CH 3COOH / CH 3COO − [CH 3COOH ]
K H 2O = [ H + ] × [OH − ] =10 −14
+ −

HA ← H + A
+ −
[ H ][ A ]
K A/ B = K = K HA =
HA / A− [ HA]
AC1 28
Dissociation constants of conjugated
base − −
CH 3COO + H 2O 
→ CH 3COOH + OH
KB

[CH 3COOH ] × [OH − ]


K =
CH 3COO − [CH 3COO − ]
[CH 3COOH ] × [OH − ] × [ H + ]
= − +
= K H 2O / K CH 3COOH
[CH 3COO ] ×[H ]

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+]

HA → H + + A− 10–2 M HCl (pH = 2)


+
k >> 0 ⇒ [ H ] ≈ C HA
H 2O → H + + OH −
Khi C HA ≈ 10 −8 − 10 −7 M
−14
+ − − 10
[ H ] = [ A ] + [OH ] H 2O = C HA + +
[H ]
+ 2 + −14
⇒ [ H ] − C HA [ H ] − 10 =0

AC1 32
Medium acid

+ − 10–2 M HIO3 (pKa =


→H +A
HA ←
0.9) (pH = 2.02)
+ −
[H ] = [ A ]

[ A ] + [ HA] = C HA

[ 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

pH of monoprotic acid (Ka1)

H2CO3 (pKa1 = 6,35, pKa2= 10,32) 10–2 M


(pH = 4.18)

AC1 35
Polyprotic acid k1 ≈ k 2

HA1←
 + −
k HA1
→ H + A1
HA2 ←
 + −
k HA2
→ H + A2

[ H + ][ A1− ] [ HA1 ] + [ A1− ] = C HA1 (3)


k HA1 = (1)
[ HA1 ]
[ HA2 ] + [ A2− ] = C HA2 (4)
[ H + ][ A2− ] + − −
k HA2 = ( 2) [H ] = [ A1 ] + [ A2 ](5)
[ HA2 ]

AC1 36
Polyprotic acid k1 ≈ k 2

+ k HA1 [ HA1 ] k HA2 [ HA2 ]


[H ] = +
+
[H ] [H + ]
⇒ [ H + ]2 = k HA1 [ HA1 ] + k HA2 [ HA2 ]
[ HA1 ] ≈ C HA1 , [ HA2 ] ≈ C HA2
⇒ [ H + ]2 = k HA1C HA1 + k HA2 C HA2

n
or [ H ] = ∑ k HAi C HAi
+ 2

i =1

AC1 37
Polyprotic acid - Example k1 ≈ k 2

acid m-phthalic, 10-2 M C6H4(COOH)2 (pKa1 =


3.70, pKa2 = 4.60) (pH = 2.87)

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

H2CO3 (pKa1= 6.35, pKa2 = 10.32)


Na2CO 3 (pKb1 = 3.68, pK b2 = 7.35)

pH of monoprotic base (pH = 11.13)

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

Weak acid and strong base


CH3COOH + NaOH CH3COONa + H2O (2)

CH3COONa 10-2 M, pH = 8.38 CH3COO-, pH < 7


Strong acid and weak base

NH4OH + HCl NH4Cl + H2O (3)


NH4Cl 10–2 M, pH = 5.62
NH4+, pH > 7
AC1 46
PH of salts

 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

 What is a buffer solution


 A solution containing a conjugate weak
acid/weak base pair that is resistant to a
change in pH when a strong acid or strong
base is added.
 Buffer solution
 HA và MA
 B và BH+
 pH of a buffer solution

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

1) Mixture of 10–2 M CH3COOH and 10–2 M


CH3COONa

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

4) How many grams of CH3COONa needed to add to the


solution (2) to have a solution of pH 5.

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

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