2, Chapter 2 69K

CONTENTS
} CHAPTER 1: THE BASIC LAWS FOR THE

ELECTROLYTES IN SOLUTION
} CHAPTER 2. ACID-BASE EQUILIBRIUM
} CHAPTER 3: COMPLEX EQUILIBRIUM
} CHAPTER 4: OXIDATION – REDUCTION

EQUILIBRIUM
} CHAPTER 5: THE EQUILIBRIUM IN SOLUTION

CONTAINING PRECIPITATE
1 Qualitative Chemical Analysis
Outline of Chapter 2
1. Acid and base concepts.
2. pH scale.
3. The Law of Conservation of Proton.
4. Acid-base equilibrium and calculating pH in solutions.
a) In monoprotic acid / monoprotic base solution.
b) In polyprotic acid / polyprotic base solution.
c) In solution contains amphiprotic substances.
5. In buffer solution.
6. Hydroxo complex formation of metal ions.
7. pH indicators.
2
Qualitative Chemical Analysis
1. Acid and Base Concepts
} Arrhenius concept－Acids produce hydrogen ion in water,
while bases produce hydroxide ions.
} Limited to aqueous solution
} One kind of base – the hydroxide ion
} Brønsted-Lowry concept－An acid is a proton (H+) donor,
and a base is a proton acceptor.
H+
Example:
CH3COOH + H2O ⇌ CH3COO− + H3O+
(acid 1) (base1) (base 2) (acid 2)
CH3COOH/CH3COO− are conjugate acid-base pair
3
1. Acids and Bases
} Conjugate base that remains of the acid molecule after a proton
is lost.
} Conjugate acid that is formed when the proton is transferred to
the base.
} Conjugate acid-base pair: HA vs. A- and H2O vs. H3O+
4
Classification of acids and bases
Acids Bases
Strong acids Weak acids Strong bases Weak base
5
2. The pH scale
The pH scale measures how acidic or basic a substance is. The pH
scale ranges from 0 to 14. A pH of 7 is neutral. A pH less than 7 is
acidic. A pH greater than 7 is basic.
pH = –lg[H+] pOH = –log[OH–]

[H+] = 10-pH pH + pOH = 14
pH value
6
2. The pH scale
pH = 6 pH = 2
pH = 13
pH = 4 pH = 5
7
2. The pH scale
} Fill in the missing information in the following table:
8
3. Conservation of proton (Điều kiện proton: ĐKP)
The content of law can be explained as following:

If we choose any state of solution as level 0 (usually choose
the initial state), total concentration of proton released by acids
(from level 0) minus total concentration of proton accepted by
bases (from level 0) equal to equilibrium concentration of
proton (at equilibrium state).
" % " %
[H ] = $ ∑[H ]i '
+ +
− $ ∑[H ]i '
+
!
# i &donor # i &accept
total concentration total concentration
of hydrogen ion of hydrogen ion
released by acids accepted by bases
Example 1. Describe equation of the conservation of proton law for
solution contains
a) C mol.L−1 CH3COOH
b) C1 mol.L−1 CH3COOH and C2 mol.L−1 CH3COONa.
Example 2: Describe equation of the conservation of proton law for
solution contains C mol.L−1 H3PO4.
H3PO4 (C M)
−H+
H2PO4−
−2H+
HPO42−
−3H+
11
Qualitative Chemical Analysis PO43−
Example 3: Describe equation of the law of conservation of proton
for solution containing C1 mol.L−1 H2SO4 and C2 mol.L−1 NH4+.
12
4. Calculate the pH of Solution
General principle
} 1. Describe all possible equilibriums.
} 2. Estimate the degree of each equilibriums to ignore the
minus equilibriums.
} 3. If all most equilibriums can be ignored, remain only one
equilibrium
} Þ Using the law of mass action.
} 4. If there are 2 or more than 2 equilibriums remain.
} Þ Using the law of conservation of proton (ĐKP).

4.1. Calculate the pH of Strong Acid Solutions
• Strong acids (HY) are subtances which could dissociate
completely and donate proton to water.
• Some common strong acids: HCl, HBr, HI, HSCN, HClO3,
HBrO4, HNO3, H2SO4 (for the first ionazation step), HClO4,
HMnO4 …
Question: Estimate pH of a solution contains C (mol L−1) strong
acid HY.
Equibriums:
HY H+ + Y− (1)
H 2O ⇌ H+ + OH− (2)
Level 0: HY, H2O
The equation of conservation of proton:
[H+] = [OH−] + [Y−], or [H+] = [OH−] + C
14
4.1. Calculate the pH of Strong Acid Solutions
* If CHY >> 10−7 M, the dissociation equilibrium of water can be
ignored à [H+] = CHY à pH = - lg CHY.
* If CHY ≈ 10−7 M à can not ignore the equilibrium of water à
using the law of mass action for water dissociation equilibrium.
* If CHY << 10−7 M à pH = 7.0.
15
Example 1: Calculate the pH of solution contains:
a) 0.10 M HCl. b) 1.0 ´ 10-7 M HCl. c) 1.0 ´ 10-9 M HCl.
16
4.2. Calculate the pH of monoprotic weak acid solutions
The weak monoprotic acid (HA) could be molecule (CH3COOH,
HNO2 …), cation (NH4+ ) or anion (HSO4−).
In solution contains weak acid HA C (M); Ka.

Equilibriums:
HA ⇌ H+ + A− Ka (1)
H2O ⇌ H+ + OH− Kw (2)
Question: Calculate the pH of solution contains C (mol/L) HA (Ka).

HA ⇌ H+ + A− Ka (1)
H2O ⇌ H+ + OH− Kw (2)
The law of conservation of protion:
[H+] = [OH-] + [A-]
17
Compare Ca .K a and KW !
Where Ca .K a ≈ [HA]. K a = [H + ][A - ] ≈ [H + ]HA

!
KW = [H + ][OH - ] ≈ [H + ]H
2O
If Ca .K a >> KW → [H + ]HA >> [H + ]H !

2O
Can ignore dissociation process of water
[H+] = [A-]
Using the law of mass action for
HA dissociation.
18
If Ca .K a ≈ KW → [H + ]HA ≈ [H + ]H !
2O
Can not ignore dissociation process of water
[H+] = [A-] + [OH-]

Using the law of conservation of proton
Method 1: + - - Ka KW
[H ] = [A ] + [OH ] = Ca +
+
[H ] + K a [H + ]
Ka K
or h = Ca + W (h = [H + ])
h + Ka h
Solving the cubic equation [H+] and pH
19
Method 2:
+ - - K a [HA] KW
[H ] = [A ] + [OH ] = +
+
[H ] [H + ]
K a [HA] KW
→ h = + →h = K a [HA] + K W (*)
h h
Step1: [HA] = Ca.
Solve the equation (*), we can get h value (h = [H+])
Step2: Recalculate of [HA] by using formula:

h
[HA] = Ca
h + Ka
20
* If [HA] » C Þ the assumption is correct

Þ pH = −lg[H+]
* If [HA] ¹ C Þ the assumption is incorrect.
Recalculate value of h from equation (*) by using [HA]
value.
Repeat the calculation until hn » hn−1 (or pHn » pHn-1)
21
How to establish the formula
[HA] = C
h
Ka + h
! ?
From the equilibrium:
HA ⇌ H+ + A− Ka
h Ka
→ [HA] = C. [A] = C.
Ka + h Ka + h
22
4.3. The fractional concentration (α)
The fractional concentration (a) of one specie is the ratio of it
concentration per total concentration of both acid and its
conjugate base.
For monoprotic acid HA
aHA + aA = 1.
aHA and aA− depend on pH of solution.
At: pH = pKa à aHA = aA- = 0.5
23
4.3. The fractional concentration (α)
Problem 1: Write the fractional concentration formulas for
following species:
a) H2A; HA− and A2− for acid H2A (Dissociation acid
constants Ka1 and Ka2).
b) H3A; H2A−; HA2− and A3− for acid H3A (Dissociation
acid constants Ka1; Ka2 and Ka3).
Problem 2: Distinguish the fractional concentration (aHA)

and dissociation degree (a) of acid HA from solution
contain C mol/L HA.
24
Example 1: Calculate the pH of a 1.00 M solution of HF
(Ka = 7.2 ´ 10-4)
25
Example 2: A solution contains CH3COOH C (M). The value pH
is 3.0. Estimate the value of C. Given by: CH3COOH: pKa = 4.76.
26
Example 3. Calculating pH of 1.0´10−4 M NH4Cl solution. Given
by: NH4+: pKa = 9.24.
27
4.4. Calculate the pH of Strong base Solutions
- Strong bases (XOH) are subtances which could dissociate
completely in water.
- Some common strong bases: NaOH, KOH, RbOH, CsOH,
Ca(OH)2, Ba(OH)2 (first dissociation step) ...
Question: Calculate the pH of solution contains C (mol.L−1) strong

base XOH.
Equibriums:
XOH X+ + OH− (1)
H 2O ⇌ H+ + OH− (2)
Level 0: XOH, H2O
The equation of conservation of proton:
[OH−] = [H+] + [X+], or [OH−] = [H+] + C
28
4.4. Calculate the pH of Strong base Solutions
Case 1: If C >> 10−7 M, the dissociation equilibrium of water can
be ignored à [OH−] = CXOH à pOH = −lg CXOH à pH.
Case 2: If C ≈ 10−7 M à can not ignore the equilibrium of water
à Using the law of mass action for water dissociation
equilibrium.
29
Example 1. Calculate the pH of solution A which received by mixing 20.05
mL 1.00´10−3 M NaOH solution and 80.00 mL 2.50´10−4 M HCl solution.
30
4.5. Calculate the pH of monoprotic weak base solutions
A weak monoprotic base (B) (can be a cation (CaOH+), anion
(CH3COO−) or molecule (NH3),...
Problem: Caculating the pH of solution contains weak base B ( C
mol.L-1, Kb = Kw/Ka) .
Equilibriums:
H 2O ⇌ H+ + OH− Kw (1)
B + H 2O ⇌ HB + OH− Kb (2)
Conservation of proton:
[H+] = [OH-] - [HB]
Or [OH-] = [H+] + [HB]
31
Compare C.K b and KW !
Where C.K b ≈ [B]. K b = [HB][OH - ] ≈ [OH - ]B

!
KW = [H + ][OH - ] ≈ [OH - ]H
2O
If C.K b >> KW → [OH − ]B >> [OH − ]H !

2O
Can ignore dissociation process of water

[OH-] = [HB]
Using the law of mass action for

equilibrium (2)
32
If C.K b ≈ KW → [OH - ]B ≈ [OH - ]H !
2O
Can not ignore dissociation process of water
Using the law of conservation of proton

Method 1:
- + KW + Kb
[OH ] = [H ] + [HB] or +
= [H ] + C
[H ] [OH - ] + K b
KW h
or = h + C
h h + Ka
Solving the cubic equation [H+] and pH

33
Method 2: KW h.[B]
h = [OH − ] - [HB] = −
h Ka
→ h 2 (1 + [B].K −1
a ) = KW
Kw
→h = (*)
1 + [B].K −1
a
Step1: Assume: [B] = C.

Solve the equation (*), we can get [H+]
Step2: Recalcule [B] by using formula:
Ka
[B] = C
h + Ka
34
* If [B] » C à the assumption is correct à pH = −lg[H+]
* If [B] ¹ C à the assumption is incorrect. Recaculate

value of h from equation (*) by using value of [B].
Repeat the calculation several times until (hn » hn−1).
35
Example 1. Calculate pH of solution containing 0.010 M NaCN,
Kb = 10-4.65.
36
Example 2. Calculate the pH of 0.010 M Na2SO4 solution
(Ka2 = 10−1.99).
37
4.6. The equilibrium in mixture of a strong acid and a
weak monoprotic acid solution
A solution containning a strong acid HY with concentration of C1
(mol.L−1) and a weak monoprotic acid HA with concentration of
C2 (mol.L−1), the ionization constant Ka.
Estimation of equilibrial concentrations and pH of solution.
Equilibriums:
HY H+ + Y− (1)
HA ⇌ H+ + A− Ka (2)
H2O ⇌ H+ + OH− Kw (3)
38
The equilibrium concentration can be estimated by using

equilibrium (2) by using the law of mass action:
HA ⇌ H+ + A− Ka
C C2 C1
[] C2−x C1 + x x
Solving the equation (*), we can get x [H+] = C1 + x.
39
The equilibrium (3) can not be ignored à calculate by using the

law of conservation of proton.
− Level 0: HY, HA, H2O
− The equation of conservation of proton:
[H+] = [OH−] + [A−] + [Y−] or [H+] = [OH−] + [A−] + C1
Or
40
Step 1: Solving the equation (**) by asuming [HA] = C2.
If [HA] » C2, assumption is valid.

If [HA] ¹ C2, assumption is incorrect.
Insert value of [HA] into equation (**) to recalcute hi.
Repeat until hn » hn−1.
41
Example 1. 50.00 mL solution A was prepared by mixing 20.00
mL 0.02 M HCl solution and 30.00 mL 0.15 M CH3COOH.
Calculate the pH of solution A.
42
4.7. Calculate the pH of solution contains 2 weak acids
Calculating the pH of solution contains 2 weak acids: HA1 (C1 M, Ka1)
and HA2 (C2 M, Ka2). Estimate the equilibrial state of solution.
Equilibriums:
HA1 ⇌ H+ + A Ka1 (1)
HA2 ⇌ H+ + A Ka2 (2)
H2O ⇌ H+ + OH− Kw (3)
- If Ka1 C1 >> Ka2 C2 ; Kw, the equilibrium (2) and (3) can be
ignored. The equilibrium concentrations can be estimated by
using the equilibrium (1) using the law of mass action.
- If Ka1C1 » Ka2C2 >> Kw Using the law of conservation of
or Ka1C1 » Ka2C2 » Kw proton.
43
44
45
Example 1. Calculate pH of solution containing 0.01 M HCOOH
(Ka1 = 10−3.75) and 0.10 M HCN (Ka2 = 10−9.35)
46
Example 2. Calculate pH of solution contains 0.010 M CH3COOH (Ka1 =
10−4.76) and 0.050 M CH3CH2COOH (Ka2 = 10−4.80).
47
4.8. The equilibrium in mixture of a strong base and a
weak monoprotic base solution
A solution containning a strong base XOH with concentration of
C1 (mol.L−1) and a weak monoprotic base A with concentration
of C2 (mol.L−1), the ionization constant Kb. Estimation of
equilibrium in solution.
Equilibriums:
XOH X+ + OH− (1)
H 2O ⇌ H+ + OH− KW (2)
A + H 2O ⇌ HA + OH− Kb = KW/Ka (3)
The equilibrium (2) and (3) can be ignored à [OH−] = C1.
48
We can ignore the equilibrium (3). The equilibrium state of

solution can be estimated by using equilibrium (2)
Solving equation (*) x [OH-] = x + C1.

49
The equilibrium (2) and (3) can not be ignored à calculate by

using the law of conservation of proton.
− Level 0: XOH, A−, H2O
− The equation of conservation of proton:
[H+] = [OH−] − [HA] - [X+] or [H+] = [OH−] − [HA] - C1
Step 1: Solving the equation (**) by assume [A] = C2 h.
50
Step 2: Check the assumption:
- If [A] » C2, assumption is valid.

- If [A] ¹ C2, assumption is not valid à insert value of [A] into
equation (**) to recalcute hi.
Repeat until hn » hn−1
51
Example 1. Calculate pH of solution containing 1.0´10−4 M NaOH
and 0.010 M NaNO2 (Kb = 10−10.71).
CNaOH = 1.0´10−4 >> 10-6,355 and 10−7 → The dissociation of

water and NO2- are neglible.
→ [OH−] = 1.0´10−4 M.
pH = 10.0
52
4.9. Calculate the pH of solution contains 2 weak bases
Calculate pH of a solution contain 2 monoprotic bases: A1 (C1 M;
KaHA1) and A2 (C2 M, KaHA2).
Equilibriums:
A 1 + H 2O ⇌ HA1 + OH− Kb1 = KW/Ka1 (1)
A2+ H2O ⇌ HA2 + OH− Kb2 = KW/Ka2 (2)
H 2O ⇌ H+ + OH− Kw (3)
Compare the values of Kb1C1; Kb2C2 and Kw
* If Kb1C1 >> Kb2C2; Kw à the equilibrium (2) and (3) can be
ignored à Using equilibrium (1) for estimation of the equilibrium
concentrations.
* If Kb1C1 » Kb2C2 >> Kw or Kb1C1 » Kb2C2 » Kw à Using the
law of conservation of proton:
[H+] = [OH−] − [HA1] − [HA2]
53
4.9. Calculate the pH of solution contains 2 weak bases
Step 1: Solving equation (*) by assuming:

[A1] » CA = C1 ; [A2] » CA = C2
Step 2: Calculate [Ai]:
If [Ai] » Ci à Assumption is correct.

If [Ai] ¹ Ci à Assumption is incorrect à recalcute hi value.
Repeat
54
until hn » hn−1.
Example 1. Calculate pH of solution contains: 0.100 M NH3 (Kb1
= 10−4.76) and 0.100 M HCOONa (Kb2 = 10−10.25).
55
Example 2. Calculate pH of solution contains: 0.100 M KCN
(pKa1 =9.35) and 0.100 M NH3 (pKa2 = 9.24).
56
4.10. THE EQUILIBRIUM IN POLYPROTIC
ACID SOLUTION
Definition: Polyprotic acids are specific acids that are capable
of losing more than a single proton per molecule in acid−base
reactions.
Example: H2CO3, H3PO4, H2S, ...
For a triprotic acid H3A, the dissociativo process can be
represented by the equations:
H 3A ⇌ H + + H 2A − Ka1 (1)
H 2A − ⇌ H+ + HA2− Ka2 (2)
HA2− ⇌ H+ + A3− Ka3 (3)
Where:
[H+] [H2A−]/[H3A] = Ka1
[H+] [HA2−]/[H2A−] = Ka2
[H+] [A3−] /[HA2−] = Ka3
57
ACID SOLUTION
Problem: Estimate the equilibrial concentrations and pH in
solution contains triprotic acid H3A (C mol L−1, dissociation
constant are Ka1, Ka2, Ka3)
H 3A ⇌ H + + H 2A − Ka1 (1)
H 2A − ⇌ H+ + HA2− Ka2 (2)
HA2− ⇌ H+ + A3− Ka3 (3)
H 2O ⇌ H+ + OH− KW (4)
Compare [H+] dissociated from (1), (2), (3) and (4) by
comparison of Ka1; Ka2; Ka3; KW.
(1) If Ka1 >> Ka2; Ka3 and CKa1 >> KW.
à the second; third dissociations and dissociation of water can be
ignored.
à the equilibrium can be estimated by using the first dissociation.
58
ACID SOLUTION
(2) If Ka1 » Ka2 » Ka3 and CKa1» KW can not ignored any
dissociation process.
à Using the law of conservation of hydrogen ion concentration
for the level 0: H3A and H2O.
[H+] = [OH−] + [H2A−] + 2[HA2−] + 3[A3−]
(*)
59
ACID SOLUTION
Step 1: Solving the equation (*) by initial assuming [H3A] = C
à Value of h.
Step 2: Confirm the assuming condition by calculate [H3A]:
+ If [H3A] » C à assumption is correct.

+ If [H3A] ¹ C à assumption is incorrect à repeat
calculation until pHn+1 » pHn.
(3) CKa1 » CKa2 >> CKa3; KW

(4) CKa1 » CKa2 » CKa3 >> KW ?
[H+] = [H2A−] + 2[HA2−]
[H+] = [H2A−] + 2[HA2−] + 3[A3−]

60
Example 1. Calculate pH and the equilibrial concentration [CO32-] in
0.010 M H2CO3 solution. H2CO3: pKa1 = 6.35; pKa2 = 10.33.
61
4.11. THE EQUILIBRIUM IN
POLYPROTIC BASE SOLUTION
Definition: Polyprotic based are specific base that are capable
of receiving more than a single proton per molecule in acid−base
reactions.
Example: CO32−, PO43−, S2−, ...
For a triprotic base A3-, the dissociation process can be
represented by following equations:
A3− + H2O ⇌ OH− + HA2− Kb1 (1)
HA2− + H2O ⇌ OH− + H2A− Kb2 (2)
H 2A − + H 2O ⇌ OH− + H3A Kb3 (3)
Where:
Kb1 = KW/Ka3 = [OH−].[HA2−]/[A3−]
Kb2 = KW/Ka2 = [OH−].[H2A−]/[HA2−]
Kb3 = KW/Ka1 = [OH−].[H3A]/[H2A−]
62
Estimate the equilibrial concentration and pH of solution
contains triprotic base A3− (C mol L−1, dissociation constant of
conjugate triprotic acid are Ka1, Ka2, Ka3)
Equilibriums:
A3− + H2O ⇌ HA2− + OH− Kb1 (1)
HA2− + H2O ⇌ H2A− + OH− Kb2 (2)
H2A− + H2O ⇌ H3A + OH− Kb3 (3)
H2O ⇌ H+ + OH− KW (4)
Compare [OH−] dissociated from (1), (2), (3) and (4) by
comparison of Kb1; Kb2; Kb3 and KW.
* If Kb1 >> Kb2; Kb3 (or Ka1 >> Ka2 ;Ka3) and CKb1 >> KW
The equilibriums (2); (3) and (4) can be ignored à Estimation of
the equilibrial concentration by using reaction (1) .
63
* If Kb1 » Kb2 » Kb3 and CKb1 » KW can not ignore any
dissociation process à Using the law of conservation of
hydrogen ion concentration for the level 0: A3− and H2O.
[H+] = [OH−] − [HA2−] − 2[H2A−] − 3[H3A]
Where [HA2−] = h[A3−]Ka3−1
[H2A−] = h2[A3−]Ka2−1Ka3−1
[H3A] = h3[A3−]Ka1−1Ka2−1Ka3−1
Kw
h = - [A3- ](h.K -1
a3 + 2h 2 -1 -1
K K
a2 a3 + 3h 3 -1 -1 -1
K a1K a2 K a3 )
h
Kw
Or h = 3- -1 -1 -1 2 -1 -1 -1
(*)
64 1 + [A ](K a3 +Qualitative
2hKChemical
a2 K a3Analysis
+ 3h K a1K a2 K a3 )
Step 1: Solving the equation (*) by initial assuming [A3-] = C à
Value of h.
Step 2: Confirm the assuming condition by calculate [A3-]:
3- K a1K a2 K a3
[A ] = C.
h 3 + K a1h 2 + K a1K a2 h + K a1K a2 K a3
+ If [A3-] » C à assumption is correct.
+ If [A3-] ¹ C à assumption is incorrect.
à repeat calculation until pHn+1 » pHn.
(3) CKb1 » CKb2 >> CKb3; KW

(4) CKb1 » CKb2 » CKb3 >> KW− ? [OH−] = [HA2−] + 2[H2A−]
[OH ] = [HA2−] + 2[H2A−] + 3[H3A]
Example 1. Calculate the concentrations of H+, HSO3- ions and pH of
0.10 M Na2SO3 solution. H2SO3: Ka1 = 10-1.76; Ka2 = 10-7.21.
66
4.12. THE EQUILIBRIUM IN AMPHOLYTE
SOLUTION
Definition: Ampholytes are amphiprotic molecules that can act
both acidic and basic role.
Some common ampholytes: H2PO42-, H2N-CH2-COOH, HS-,
HCO3-,...
Estimate the equilibrium and pH of solution contains the
ampholyte NaHA C mol/l. (H2A: Ka1 and Ka2).
The equilibriums:
HA− ⇌ H+ + A2− Ka2 (1)
HA− + H ⇌ H 2A K (2)
H 2O ⇌ H+ + OH− Kw (3)
The law of conservation of proton with the level 0: HA−, H2O.
[H+] = [OH−] + [A2−] – [H2A]
67
4.12. THE EQUILIBRIUM IN AMPHOLYTE
SOLUTION
* If Kw << Ka2C and Ka1-1C >> 1 (Ka1 << C)
* If not, solving equation (*) by assuming [HA-] = C → h value.

* Check assumption condition by recalculating [HA-]
K a1h * If [HA-] = C → Assumption is correct.
−
[HA ] = C 2 !
h + K a1h+K a1.K a2 * If [HA-] ≠ C → Assumption is not correct.
68
Example 1: Calculate pH of solution containing 1.00´10−2M
NaHS (Ka1 = 10−7.02; Ka2 = 10−12.9).
69
Example 2. Calculate pH of 0.10 M NH4HCO3 solution.
Ka(NH4+) = 10−9.24; Ka1(H2CO3) = 10−6,35; Ka2(H2CO3) = 10−10.33.
70
5. BUFFER SOLUTIONS (SEMINAR)
71
6. The formation hydroxo complex of metal ions
The formation of an hydroxo−complex is a typical example of an
hydrolysis reaction.
Mn++ H2O ⇌ MOH(n−1)+ + H+ *b1
Mn++ 2H2O ⇌ M(OH)2(n−2)+ + 2H+ *b2
Mn+ plays as weak acid; and *b ~ Ka
In solution, Fe3+ ion can form following hydroxo complexes:
Fe3+ + H2O ⇌ FeOH2+ + H+ lg*b1 = −2.17
2Fe3+ + 2H2O ⇌ Fe2(OH)24+ + 2H+ lg*b2 = - 2.85

Example 1. Calculate pH of 0.010M Ni(ClO4)2 solution *b = 10−8.94
Ni2+ + H2O ⇌ NiOH+ + H+ *b = 10−8.94

Example 2. Calculate pH of 0.010M Fe(NO3)3 solution.
Fe3+ + H2O ⇌ FeOH2+ + H+ lg*b1 = −2.17
2Fe3+ + 2H2O ⇌ Fe2(OH)24+ + 2H+ lg*b2 = - 2.85

Topic 1: Buffer solution
} What is buffer solution?
} Composition of buffer solution?
} Properties of buffer solution.
} Application of buffer solution.
} Calculate the pH of buffer solution by using Henderson –
Hasselbalch equation.

Topic 2: Prepare buffer solutions
Britton–Robinson buffer is a "universal” pH buffer used for the
range pH 2 to pH 12. Universal buffers consist of mixtures of acids
of diminishing strength (increasing pKa) so that the change in pH is
approximately proportional to the amount of alkali added.
Using distilled water and stock solutions as following: H3BO3 0.50
M; H3PO4 0.50 M; CH3COOH 0.50 M and KOH 1.00 M.
Describe the method to prepare 1,00 liter of each buffer solution
with pH = 4,00; 7,00 and 9,00.
In each of buffer solution: The initial concentration of H3BO3 =
0.020 M; The initial concentration of H3PO4 = 0.020 M;
CH3COOH = 0.020 M.

Topic 3: pH indicator (acid – base indicator)
} What is a pH indicator?
} Give some common pH indicators.
} How do pH indicators work?
} Application of pH indicator.
} Introduce some natural pH indicator.

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CONTENTS

} CHAPTER 1: THE BASIC LAWS FOR THE

} CHAPTER 2. ACID-BASE EQUILIBRIUM

} CHAPTER 3: COMPLEX EQUILIBRIUM

} CHAPTER 4: OXIDATION – REDUCTION

} CHAPTER 5: THE EQUILIBRIUM IN SOLUTION

CH3COOH/CH3COO− are conjugate acid-base pair

Strong acids Weak acids Strong bases Weak base

pH = –lg[H+] pOH = –log[OH–]

The content of law can be explained as following:

13 Qualitative Chemical Analysis

* If CHY << 10−7 M à pH = 7.0.

In solution contains weak acid HA C (M); Ka.

Question: Calculate the pH of solution contains C (mol/L) HA (Ka).

Where Ca .K a ≈ [HA]. K a = [H + ][A - ] ≈ [H + ]HA

If Ca .K a >> KW → [H + ]HA >> [H + ]H !

Can ignore dissociation process of water

Can not ignore dissociation process of water

[H+] = [A-] + [OH-]

Step2: Recalculate of [HA] by using formula:

* If [HA] » C Þ the assumption is correct

Problem 2: Distinguish the fractional concentration (aHA)

Question: Calculate the pH of solution contains C (mol.L−1) strong

Where C.K b ≈ [B]. K b = [HB][OH - ] ≈ [OH - ]B

If C.K b >> KW → [OH − ]B >> [OH − ]H !

Can ignore dissociation process of water

Using the law of mass action for

Can not ignore dissociation process of water

Using the law of conservation of proton

Solving the cubic equation  [H+] and pH

Step1: Assume: [B] = C.

* If [B] » C à the assumption is correct à pH = −lg[H+]

* If [B] ¹ C à the assumption is incorrect. Recaculate

The equilibrium concentration can be estimated by using

Solving the equation (*), we can get x  [H+] = C1 + x.

The equilibrium (3) can not be ignored à calculate by using the

If [HA] » C2, assumption is valid.

The equilibrium (2) and (3) can be ignored à [OH−] = C1.

We can ignore the equilibrium (3). The equilibrium state of

Solving equation (*)  x  [OH-] = x + C1.

The equilibrium (2) and (3) can not be ignored à calculate by

Step 1: Solving the equation (**) by assume [A] = C2  h.

- If [A] » C2, assumption is valid.

CNaOH = 1.0´10−4 >> 10-6,355 and 10−7 → The dissociation of

Step 1: Solving equation (*) by assuming:

Step 2: Calculate [Ai]:

If [Ai] » Ci à Assumption is correct.

+ If [H3A] » C à assumption is correct.

(3) CKa1 » CKa2 >> CKa3; KW

[H+] = [H2A−] + 2[HA2−] + 3[A3−]

(3) CKb1 » CKb2 >> CKb3; KW

* If Kw << Ka2C and Ka1-1C >> 1 (Ka1 << C)

* If not, solving equation (*) by assuming [HA-] = C → h value.

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Solving the cubic equation [H+] and pH

Solving the equation (*), we can get x [H+] = C1 + x.

Solving equation (*) x [OH-] = x + C1.

Step 1: Solving the equation (**) by assume [A] = C2 h.