CHAPTER 2.

ACID-BASE
EQUILIBRIUM AND TITRATION

NGUYEN TIEN GIANG, Ph.D

Email: ntgiang@hcmute.edu.vn
 Contents
✓Acid-base equilibrium (cân bằng acid-base)
▪ Chemical equilibrium (cân bằng hóa học)
▪ Acid-base and pH calculation (acid-base và cách tính pH)
▪ Buffer (hệ đệm)

✓Acid-base titration (chuẩn độ acid-base)

▪ Indicators (chất chỉ thị)

▪ Titration curves (đường cong chuẩn độ)

▪ Titration errors and evaluation (Sai số chuẩn độ và đánh giá sai

số)
ACID-BASE EQUILIBRIUM
(Cân bằng acid-base)
 ACID-BASE
Bronsted theory
✓ Acid is a substance that can release proton (H 3O+, hydronium ion, H+)

HCl + H2O H3O+ + Cl- Al3+ + H2O H3O+ + AlOH2+

✓ Base is a substance that can accept proton (H+ or H3O+)

CO32- + H+ HCO3-
NaOH + H+ Na+ + H2O
(CO32- + H2O HCO3- + OH-)

Acid and base can be in form of cation and anion

✓ Hydrolysis of an cation: serving as an acid
NH4+ + H2O H3O+ + NH3

✓ Hydrolysis of an anion: serving as a base

CH3COO- + H2O CH3COOH + OH-
 Phân loại acid/base
H3PO4
Acid/base được phân loại:
- Acid/base mạnh: phân ly hoàn toàn trong nước
- Acid/base yếu: phân ly một phần trong nước

Acid/base mạnh:

HCl + H2O → H3O+ + Cl- H2O

NaOH + H2O → Na+ + OH-

Acid/base yếu:
 CHEMICAL EQUIBLIRIA
Dissociation constant (hằng số phân ly)
❖ If A and B form only product AB
AB A + B
[A] [B]
K = K: dissociation constant
[AB]

K Stability of AB AB: high dissociation

p function: pK = -lgK K large pK small

Examples:
pKa (HF) = 3.2 Dissociation: HF > CH3COOH

pKa (CH3COOH) = 4.75 Acidic strength: HF > CH3COOH

6
 ❖ If A and B form n products ABn
[ABn-1][B]
Step 1 ABn ABn-1 + B K1 =
[ABn]
[ABn-2][B]
Step 2 ABn-1 ABn-2 + B K2 =
[ABn-1]
…

[AB][B]
Step n-1 AB AB + B Kn-1 =
2 [AB2]
A [A][B]
Step n AB + B Kn =
[AB]
In general: K for step 1 > step 2 > …> step n
K1 > K2 > … > Kn-1 > Kn pK1 < pK2 < … < pKn-1 < pKn
For example: H3PO4 ↔ H2PO4- + H+ pKa1 = 2.12
H2PO4- ↔ HPO42- + H+ pKa2 = 7.21

HPO42- ↔ PO43- + H+ pKa3 = 12.687

 Conjugate acid/base pair

A conjugate base is formed when an acid loses a proton

A conjugate acid is formed when a base accepts a proton

 HA + H2O H3O+ + A-
HA/A- : conjugate pair
 A- + H 2O HA + OH- (cặp acid-baz liên hợp)

8
Example 1: Find correct acid/base conjugate pair

HCl HCl Cl- ✓ HCl H+ + Cl-

NH4Cl NH4+ Cl- X NH4Cl NH4+ + Cl-

NH4+ NH3 ✓ NH4+ ↔ NH3 + H+

H2CO3 CO32- X
H2CO3 H2CO3 HCO3- ✓ H2CO3 ↔ HCO3- + H+
HCO3- CO32- ✓ HCO3- ↔ CO32- + H+
Example 2:

pKa (HF) = 3.2 pKb = 10.8 Acid strength: HF > HCN

pKa (HCN) = 9.4 pKb = 4.6 Base strength: F- < CN-

9
QUESTION
What are values using for
determine the strength of an acid
or base?
A. pH
B. Acid dissociation constant, Ka
C. pOH
D. Base dissociation constant, Kb
❖ Ion-product constant for water (tích số ion của nước)

H2O ↔ H+ + OH-

K=
H OH 
+
=K
−
= 1.8 10−16 at 22oC
H 2O H 2O

1 L of water have 55.5 moles of water

  
 H + OH − = 1.8 10 −16  55 .5  10 −14

Kw is an ion-product constant for water:

Kw = H  OH  = 10
+ − −14

11
 Acid and base dissociation constant
 HA + H 2O H 3 O+ + A-
[A-] [H3O+]
Ka =
Ka: acid constant [HA]

 A- + H2O HA + OH-
[HA] [OH-]
Kb =
Kb: base constant [A-]

Relation between
=
A H O  HAOH 
− +
= H O OH 
−
+ −

A 
3
K a Kb
Ka and Kb: HA − 3

−14
K w = K a K b = 10 E.g. Acid CH3COOH has pKa = 4.75
pK a + pKb = 14 → pKb = 14 – 4.75 = 9.25 → Kb = 10-9.25

Kb = [CH3COOH]{[oh-]
CH3COO- + h2O <-> CH3COOH + OH- 12
[CH3COO-] = 10-9.25
 pH of a strong acid and base
❖ Two equilibrium reactions occur in solution:
HA H+ + A- H 2O H+ + OH-
Ca

At Ca  10-6 M, the dissociation of water can be negligible

[H+] = Ca pH = -lgCa

❖ Similar for the case of a strong base

BOH B+ + OH-
Cb Cb

[OH-] = Cb pOH = -lgCb

Chú ý: đổi giá trị pOH → pH 13
 pH of a weak acid

↔
[H+][A-] [HA]
HA H+ + A- Ka = [H+] = Ka
Ca [HA] [A-]
H 2O H+ + OH-   
K w = H + OH − = 10 −14

[HA] C - [A-]
[H+]
=Ka - =Ka a [H+]2 = Ka(Ca – [A-])
[A ] [H+]

At Ca large, pKa <9, [H+] from the dissociation of water and

[A-] << Ca can be negligible

[H+] = KaCa pH = ½(pKa + pCa)

14
Example

AT CLASS: (a)
AT HOME: (b), (c)
 pH of a weak base

B + H20 BH+ + OH-

[BH+][OH-]
Kb =
[B]
H 2O H+ + OH-

❖ Similar to the calculation of a weak acid

[OH-] = KbCb pOH = ½(pKb + pCb)

NH3 nồng độ 10-2 M,

tính pH của dung dịch này?

Student learn it at home! 16

 pH of a polyprotic acid
[H+] [HA-]
H 2A H+ + HA- Ka1 =
[H2A]
HA- H+ + A2- [H+] [A2-]
Ka2 =
[HA-]
H 2O H+ + OH-

[H+] = [H+1] + [H+2] . (Skip [H+] of H2O)

With Ka1 >> Ka2 (Skip [H+2] next to [H+1 ]

=
(H + H ) H 
+
1
+
2
 H 
+
2 +
Ka2
H  +
1
2

[H+] = [H+1] + Ka2

pH of a diprotic base Similar to the case of a diprotic acid

17
 pH of a salt solution
❖ Salt is produced from a strong acid and a weak base, pH < 7

NH4Cl → NH4+ + Cl-

NH4+ ↔ H+ + NH3 pKa = 14 – pKb-NH3

Similar to the case of a weak acid

❖ Salt is produced from a strong base and a weak acid, pH > 7

CH3COONa → CH3COO- + Na+

CH3COO- + H2O ↔ OH- + CH3COOH

pKb = 14 – pKa-CH3COOH
Similar to the case of a weak base

18
 NH4+ + H2O↔ NH3 + H3O+ pKa = 9.25
CH3COO- + H2O ↔ CH3COOH + OH- pKb = 9.25

H2C2O4 + H2O ↔ HC2O4- + H3O+ pKa1 = 1.27

HC2O4- + H2O ↔ C2O42- + H3O+ pKa2 = 4.27

HC2O4- +H2O <-> H2C2O4 + OH pKb = 12.73

H3PO4 ↔ H2PO4- + H+ pKa1 = 2.12

H2PO4- ↔ HPO42- + H+ pKa2 = 7.21
HPO42- ↔ PO43- + H+ pKa3 = 12.68

CH3COO-
 Xác định dạng tồn tại chính của acid/base theo pH
Với acid đơn chức:

pH [A-] : [HA]
pKa -2 1:100
pKa – 1 1:10
pKa 1
pKa + 1 10:1
pKa + 2 100:1

Dạng tồn tại chính của acid benzoic tại pH = 9 ??

Xác định dạng tồn tại chính của acid/base theo pH
Với acid đa chức
 BUFFERS
- A buffered solution: is mixture of a weak acid and its conjugate base. DD
đệm là hỗn hợp của 1 acid và base liên hợp của nó.
Examples: CH3COOH/CH3COONa, NH4Cl/NH3.

- A buffered solution resists changes in pH when acids or bases are

added or when dilution occurs. Dung dịch đệm có tác dụng duy trì
pH của dung dịch khi thêm acid, base, hay khi pha loãng dung dịch

pH của dung dịch đệm

A buffer
HA
NaA
H 
+
= Ka
Ca
Cb
pH = pK a + lg
Cb
Ca

25
The effect of added acids and bases

H +
= Ka
Ca
Cb

▪ Adding H+ A- + H+ → HA

Ca +  H + 
 H +  = Ka added
buffer
Cb −  H + 
added

▪ Adding OH- HA + OH- → A- + H2O

C − 
 OH −

 H  buffer = K a
+ a added

Cb + OH − 
added

26
Ví dụ 1: Dung dịch A được chuẩn bị bằng cách trộn 100 ml dd
CH3COOH 0.2M và 100 ml dd CH3COONa 0.2M.
a. Tính pH của dung dịch A.
b. Thêm vào dd A 5 ml dd HCl 0.1M. Hãy tính pH của dd thu được.
c. Thêm vào 200 mL nước 5 mL dd HCl 0.1M. Tính pH?
d. Thêm vào dd A 5 ml dd NaOH 0.1M. Hãy tính pH của dd thu được.
e. Thêm vào dd A 10 ml nước. Hãy tính pH của dd thu được.

200 mL, CH3COOH = 0.1 M, CH3COONa = 0.1 M

H 
+
= Ka

Ca − OH − 

Cb + OH − 
27
 Buffer capacity (đệm năng)
A measure of how well a solution resists changes in pH when strong
acid or base is added
Cb Ca Ca Cb
= =− = 2.303
pH pH Ca + Cb

max ↔ Ca = Cb = Co/2 ↔ Ca/Cb = 1

1 Ca
 is effective as   10
10 Cb
Cb
pK a − 1  pH  pK a + 1 pH = pK a + lg
Ca
Seek acid whose pKa is as close as possible to the desired pH.
The useful pH range of a buffer is usually considered to be pKa
± 1 pH unit.
28
Ví dụ 1: pha 1L dung dịch đệm có pH = 5

Ví dụ 2: Để điều chế dung dịch đệm pH 4.5 cần sử dụng dung dịch
acid nào sau đây:

a. CH3COOH b. C2H5OCOOH

c. NH4+ d. HCN
pKa-CH3COOH = 4.75, pKa-C2H5OCOOH = 3.6, pKa-NH4 = 9.25, pKa-HCN = 9.32
 pKb of NH3= 4.75

(a) pOH = ½ (pKb + pCb) = ½(4.75 + 1) =a

pH = 14 – a =b

AT CLASS: (a)
AT HOME: (b), (c)
pKa + pCa)

Ka = 1.8x10-4

e) Mixed with 25 mL of 0.1 M NaOH solution

.

AT CLASS: (b) (c) (d)

AT HOME: (a)
 HOMEWORK

NH3: pKb = 4.75, NH4+: pKa = 14 – 4.75= 9.25

HOMEWORK

Ka = 1.38x10-4
HOMEWORK
HOMEWORK
ACID-BASE TITRATION
 RULES

Titration methods are based on determining the quantity of a

reagent of known concentration that is required to react
completely with the analyte.

➢ Volumetric titrations: measuring the volume of a reagent

➢ Gravimetric titrations: measuring the mass of a reagent
➢ Columetric titrations: the "reagent" is a constant direct electrical
current of known magnitude that consumes the analyte
TERMS A standard solution (or a standard titrant) is a
reagent of known concentration that is used to
carry out a volumetric titration

▪ Titration
Standard solution
Reaction:
(standard Titrant)
X+ R → C + D
Known Concentration ▪ Theo equivalence
law
eqX= eqR
Analyte Solution: CR .VR
unknown CX =
concentration VX
INDICATOR
 BEHAVIOR OF ACID-BASE TITRATION
Neutralization of acid and base

H+ + OH- = H2O
HA + OH- = A- + H2O
Contents:

✓ pH Indicators (chất chỉ thị pH)

✓Titration Curves (đường cong chuẩn

độ)

✓Titration Errors and evaluation

(sai số trong chuẩn độ)

 pH indicator

Ví dụ: chuẩn độ HCl bằng NaOH Tại sao chất chỉ thị pH đổi màu
- Trong erlen: acid HCl, chất chỉ thị khi pH thay đổi ????
- Trên buret: NaOH

2/2015
 pH indicators
Indicators are weak organic acid or weak base that color of
molecular differ from the color of ion
HIn ↔ In- + H+

Range of color change

▪ Range of color change : pHI → pHII (pKa,In-1 → pKa,In+1)

• ΔpHIn = pHII – pHI = 2: range of color change
• Range of color change detected by an average observer
• ΔpHIn is smaller → color change is clearer
42
 pT of indicator

Chỉ số pT của chị thị pH

- pHI < pH < pHII ➔ màu trung gian
- Chọn màu nhạy nhất lấy làm mốc để dừng chuẩn độ, gọi là pT
- pT = pHend point: dừng chuẩn độ
 Principle of choosing indicator

- Build a titration curve

- Determine the pH at F = 0.99 and F = 1.01
- pHF=0.99 – pHF1.01: Titration jump (bước nhảy chuẩn độ)

Choosing an indicator:

pHF=0.99 < pT < pHF=1.01

F = 1.01
(or pHF=0.999 < pT < pHF=1.001) Equivalence point pT
F = 0.99

How to build a titration curve??

How to build titration curve

* Graph of pH – V; or pH- P (P=(CVi /C0V0)

* Computing the values of pH in the titration: (1) pre-
equivalence, (2) equivalence, and (3) post-equivalence.
- Initial point: don’t add titrant to analyte solution
- Pre-equivalence: add titrant at 50%, 90% or 99% titration fraction
- Equivalence: add titrant at 100% of titration
- Post-equivalence: add titrant at 101%, 110%, 200%
→ Calculate these values and graph the pH – V (titration curve).
TITRATION OF A STRONG ACID

− Titrant is a strong base solution: NaOH or KOH

− Titration reaction: H+ + OH- → H2O
Co,Vo C,V

The accuracy of the titration depends on the level of acid

concentration → [Acid] ≥ 10-3M.

− pHeq = 7  pT < pHeq → negative error

pT > pHeq → positive error

46
 Titration curve of a strong acid by a strong base
Ví dụ: Thêm 100 mL NaOH 0.5 M vào 100 mL dung dịch HCl 1 M, tính nồng độ H+ ?

H+ + OH- → H2O
Co,Vo C,V

- Nồng độ H+ sau khi pha loãng dung dịch

Đặt hệ số pha loãng (D):
CoVo = CsVs
Vo C
CoVo = Cs.(Vo+V) → Cs = Co*Vo/(Vo+V) DF = =
Vo + V FCo + C

→ Cs = Co.D
CoVo CoC 1*100 1* 0.5
Cs = = Cs = = = 0.5
Vo + V FCo + C 100 + 100 0.5*1 + 0.5

- Nồng độ H+ còn lại sau khi phản ứng với OH-: = Cs.(1-F)

CoC (1 − F )
[H + ] = [H+ = 0.5*(1-0.5) = 0.25 M
2/2015 FCo + C
Compute a titration curve of a strong acid by a strong base

H+ + OH- → H2O
Co,Vo C,V

F Property pH

0 H+ pH = -logCo

0<F<1 H+

0.99 H+

1 Neutral 7

1.01 OH-

>1 OH-

2/2015
Problem: Titration of a HCl solution of about 0.1N using a
0.1 N NaOH solution as a titrant. Analyze the titration?
Solution
Titration reaction:
H+ + OH- → H2O
F = 0.99 pH = pCo + pDF + 2 = 1 + 0.3 + 2 = 3.3
F = 1.00 pH = 7
F = 1.01 pH = 14 – (pCo + pDF + 2)
= 14 – (1 + 0.3 + 2) = 10.7
Choosing indicator with in range of 3.3 < pT < 10.7
Metyl orange has pT = 4 (sai số thiếu),
phenolphtalein pT = 9 (sai số thừa). 49
50
Titration curves for HCl with NaOH.
Curve A: 50.00 mL of 0.0500 M HCl with 0.1000 M NaOH.
Curve B: 50.00 mL of 0.000500 M HCl with 0.00100 M NaOH

- Equivalence point: pH=7

- Smaller titration jump for the
lower conc. of the reagent
- Indicator is not critical when the
reagent conc. is ~0.1 M
- But, at low conc., bromocresol
green and phenolphthalein are
not suitable (transition range is
outside titration jump)
 TITRATION OF A STRONG BASE
Students learn ebook at home and do homework
 TITRATION OF A WEAK ACID

HA + OH- → A- + H2O
Co,Vo C,V

− Titrant is a strong base solution: NaOH or KOH

− Indicator: HIn ↔ H+ + In-

Acid color Base color

Choosing indicator pHF=0.99 < pT < pHF=1.01

54
Compute a titration curve of a single weak acid by strong base

HA + OH- ↔ A- + H2O
Co,Vo C,V

F Property pH

0 HA pH = 0.5(-logKa - logCo)

0<F<1 HA/A-

0.99 HA/A- pH = -logKa + 2

1 A-

1.01 OH-, A-

>1 OH-, A-

2/2015
 The effect of acid concentration

Titration jump =
equivalence point region

Titration jump in A
curve is longer than that
of in B curve.

Curve for the titration of acetic acid with NaOH

Curve A: 0.1000 M acid with 0.1000 M base.
Curve B: 0.001000 M acid with 0.001000 M base.
 The effect of acid strength
Ka.Ca  10-8

Each curve represents the titration of 50.00 mL of 0.1000 M

weak acid with 0.1000 M strong base.
 TITRATION OF A WEAK BASE
Students learn ebook at home and do homework

HOMEWORK
HOMEWORK
HOMEWORK
 TITRATION OF A POLYFUNCTIONAL ACID

H2A + OH- → HA- + H2O

Co,Vo C,V
HA- + OH- → A2- + H2O
− Indicator: HIn ↔ H+ + In-
Acid color Base color
Choosing indicator :
First titration point : pHF=0.99 < pT1 < pHF=1.01
Second titration point : pHF=1.99 < pT2 < pHF=2.01

Important Notes:
1. pka2 – pka1 ≥ 4: Possible to separately titrate first steps and second steps
2. Ca.Ka ≥ 10-8: possible to titrate
63
64
 Calculate pH at equivalance point and choose
indicator

pH= ½ (pKa1 + pCa) pH= 7 + ½ (pKa3 +lgCb)

1st equivalence 2st equivalence

point (NaH2PO4) point (Na2HPO4)
Compute a titration curve of a polyfunctional weak acid by strong base

Step 1: H3A + OH- ↔ H2A- + H2O

Step 2: H2A- + OH- ↔ HA2- + H2O
Co,Vo C,V

F Property pH

0 H3A pH = 0.5(-logKa1 - logCo)

0<F<1 H3A/H2A-

0.99 H3A/H2A- pH = -logKa1 + 2

1 H2A-

1.01 H2A+/HA2- pH = -logKa2 – 2

1<F<2 H2A+/HA2-
2/2015
 Compute a titration curve of a polyfunctional weak acid by strong base

F Property pH

1.99 H2A+/HA2- pH = -logKa2 + 2

2 HA2-

2.01 HA2-/A3- pH = -logKa3 – 2

2<F<2.5 HA2-/A3-

2/2015
 Evaluation Titration H3PO4 with NaOH

Ka1 > Ka2 often by a factor of 104 to 105 : can titrate first
step and second step, respectively

Ka3 = 10-13 : so small (Ca.Ka <10-8 ) extremlely weak, can not

titrate in third step
V2 2 V1
TITRATION OF A POLYFUNCTIONAL BASE
• d) Evaluation:

• V2 V1?

-e) Choosing indicators:

First step:

Second step
 TITRATION OF A MIXTURE OF A STRONG
ACID AND WEAK ACID

Titration a mixtures of HCl and H3PO4 by NaOH

HCl + NaOH = NaCl + H2O Khoảng bước nhảy

của H3PO4
H3PO4 + NaOH = NaH2PO4 + H2O

Khoảng bước nhảy

NaH2PO4 + NaOH = Na2HPO4 + H2O
của H2PO4-

2008- 2009
]
Titration curve

VOH- chuẩn nấc 2 H3PO4: = V2-V1 = A

VOH- chuẩn HCl: = V1-A
• d) Evaluation:

• V2??? 2V1?

-e) Choosing indicators:

First step:

Second step:
TITRATION OF A MIXTURE OF A STRONG
BASE AND WEAK BASE

Titration a mixtures of NaOH and Na2CO3 by HCl

NaOH + HCl = NaCl + H2O Khoảng bước nhảy

Na2CO3 + HCl = NaHCO3 + NaCl của CO32-

Khoảng bước nhảy

NaHCO3 + HCl = CO2 + H2O + NaCl của HCO3-
• d) Evaluation:

• V2??? 2V1?

-e) Choosing indicators:

First step:

Second step:
Titration curve

VH+ chuẩn nấc 2 CO32-: = V2-V1 = A

2008- 2009 VH+ chuẩn NaOH: = V1-A
]
HOMEWORK
HOMEWORK
HOMEWORK
2008-2009
Calculate the pH of the solutions:

a) 0.100 M NaOCl

b) 0.200M NH3 and 0.400M NH4Cl

c) 0.100 M HOC2H4NH3+

d) mixed 40,0 mL of 0,100M NaOH with 60,0 mL of 0.100M HCl

d) 0.0100 M NaNO3