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Acid – Base

Mr. Kiattisak Thaveekham, Lecturer.

 Acids – Bases Theory


 Arrhenius, 1880s

Acid = substance dissolve in water , H+

Base = substance dissolve in water , OH–

Ex. HCl(g) H


2O
 …………. + ……………

NaOH(s) H
2O
 …………. + ……………

 BrØnsted – Lowry, 1923

Acid = H+ donor.

Base = H+ acceptor.

Ex. HCl(aq) + H2O(l) 


 …………. + ……………

NH3(aq) + H2O(l) …………. + ……………

HCN(aq) + NH3(aq) NH4+(aq) + CN – (aq)

 Conjugate acid – base pairs =……………………………………………………..

 Lewis

Acid = electron pair acceptor.

Base = electron pair donor.

H+(aq) + OH – (aq) H2O(l)

-
AlCl3(g) + Cl– (g) 
 g
CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 2

 Strength of Acids and Bases


Acids and bases are classified as strong or weak, depending on the extent to which they are
ionized in solution

Strong acids are strong electrolytes that ionize completely in water.

HCl(aq) + H2O(l) 
 …………. + …………… (complete ionization)

we use H3O+ and H+ interchangeably to represent the hydrated proton in water. Thus, we can
simplify this acid ionization equation to

HCl(aq) 
 …………. + ……………

HBr(aq) 
 …………. + ……………

HI(aq)  H+(aq) + I – (aq)


HClO4(aq) 
 …………. + ……………

HNO3(aq) 
 …………. + ……………

H2SO4(aq) 
 …………. + ……………

Strong bases are strong electrolytes that ionize completely in water.

Hydroxides of alkali metals(all 1A), such as NaOH, KOH.

Hydroxides of alkaline earth metals(some 2A), such as Ca(OH)2, Sr(OH)2, Ba(OH)2.

NaOH(s) H
2O
 …………. + ……………

KOH(s) H
2O
 K+(aq) + OH – (aq)

Ca(OH)2(s) H
2O
 …………. + ……………

Ba(OH)2(s) H
2O
 …………. + ……………

Weak acids only partially dissociates in aqueous solution,

such as …………………………….…………………………………………

HA(aq) …………. + ……………

or HA(aq) + H2O(l) …………. + ……………

Ka = ………………………… or Ka = …………………………
CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 3

Weak base such as …………………………….………………………

NH3(aq) + H2O(l) …………. + ……………

Kb = …………………………

Molecular structure affect strength of acid


3.1 . Binary acid, HX. The strength of the acid is measured by its tendency to ionize

 H+ + X–

Factors : 1. Strength of bond

2. Bond polarity

 In the same group of X in HX

……………………………………………. is the major factor determining acid strength

TABLE : Bond enthalpies for hydrogen halides and acid strength

Bond enthalpy
Substance Acid strength
(kJ/mol)
HF 568.2
HCl 431.9
HBr 366.1
HI 298.3

 In the same period of X in HX

…………………………….. is the major factor determining acidity.

For example CH4 ……. N 3 ……. 2O ……. HF

Increasing acid

4A 5A 6A 7A
CH4 NH3 H2O HF

Neither acid Weak base Weak acid


nor base Kb = 1.8 x 10-5 Ka = 6.8 x 10-4
SiH4 PH3 H2S HCl
Increasing acid

Neither acid Very weak base Weak acid Strong acid


nor base Kb = 4 x 10-28 Ka = 9.5 x 10-8
H2Se HBr

Weak acid Strong acid


Ka = 1.3 x 10-4

FIGURE: Trends in acid strength for binary hydrides.


CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 4

3.2. Oxoacids (or Oxyacids), HmXOn . The presence of one or more O – H bonds.

X O H

Carbonic acid, H2CO3

 In the same group of X (the same oxidation number)

acid strength increases with increasing …………………………… of the centra atom .

HmXOn EN of X Ka Acid strength


-8
HClO 3.0 x 10
HBrO 2.5 x 10-9
HIO 2.3 x 10-11

 In the same central atom (X) but different numbers of attached groups.

acid strength increases as the …………………………………. of the central atom increases.

hypochlorous acid chlorous acid chloric acid perchloric acid

HClO HClO2 HClO3 HClO4

3.3 Carboxylic acids, RCOOH .

The strength of carboxylic acids depends on the nature of the …………………………….

Lewis structure formic acid, HCOOH acetic acid, CH3COOH

benzoic acid, C6H5COOH chloroacetic acid, ClCH2COOH


CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 5

The autoionization of water


H2O(l) H+(aq) + OH – (aq)

or H2O(l) + H2O(l) H3O+(aq) + OH– (aq)

Kw =…………………………… or Kw =……………………………

Kw is called the ion-product constant

In pure water at 25 °C Kw = ……………………………= ……………………………

If [H+] = [OH – ] = ……… ……………………………

[H+] > [OH –] ……………………………

[OH –] > [H+] ……………………………

pH scale
pH of a solution is defined as the negative logarithm of the hydrogen ion concentration

pH = -log[H+] or pH = -log[H3O+]

Likewise, pOH = -log[OH–]

pKa = -logKa

Consider the ion-product constant for water at 25°C :

Kw = [H+][OH –] = 1.0 x 10-14

-log ([H+][OH –]) = -log (1.0 x 10-14)

-log[H+] - log[OH –] = -log(1.0) - log(10-14)

pH + pOH = 14

pH scale

Increasing acid Increasing base


Neutral
CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 6

The relationship between Ka and Kb


Consider the CH3COOH and CH3COO – conjugate acid – base pair. Each species reacts with
water:

[H ][CH3 COO ]


(1) CH3COOH(aq) CH3COO –(aq) + H+(aq) : Ka 
[CH3 COOH]

[CH3 COOH][OH ]
(2) CH3COO –(aq) + H2O(l) CH3COOH(aq) + OH–(aq) : Kb 
[CH3 COO ]

(1)+(2) : H2O(l) H+(aq) + OH – (aq)

[H ][CH3 COO ] [CH3 COOH][OH ]


K a K b  
[CH3 COOH] [CH3 COO ]

Ka x Kb = [H+][OH – ]

Ka x Kb = ……….

Ka x Kb = ……………………… at 25 °C

Expressing equation as : Ka =…………………. and Kb =………………….

Equation can be written in terms of pKa and pKb : pKa + PKb = pKw = 14 at 25 °C

Percent ionization
[ionized]
percent ionization  100%
[initial]

 Conclusion
CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 7

EXERCISE 1.
1. Arrange the compounds in each series in order of increasing acid strength
(a) HBr, KH, AsH3, H2Se =………………………………………………………………..

(b) H2SO4, H2SeO4, H2SeO3 =………………………………………………………………..

2. For each reaction. Predict whether the equilibrium lies to the left or to the right
(a) CH3COOH(aq) + HCOO –(aq) CH3COO–(aq) + HCOOH(aq)

- - - -
(b) O (a ) + O a O a O (a )

- -
(c) PO (a ) + O PO a + O (a )

+
(d) N (a ) + O a N a O

3. Calculate the pH of a 0.01 M HCl solution and 0.01 M Ca(OH)2 solution.


CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 8

4. An aqeous solution of HNO3 has a pH of 2.0 , calculate the concentration in mol/L of HNO3.

5. What is the pH of a 0.036 M nitrous acid (HNO2) solution whose Ka is 4.5 x 10-4 ?
CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 9

6. What is the pH of a 0.20 M ammonia solution whose Kb is 1.8 x 10-5 ?

7. The pH of a 0.20 M formic acid solution is 2.23. What is the Ka of formic acid ?
CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 10

8. Calculate the concentration of all the species present at equilibrium in a 0.10 M oxalic acid
(H2C2O4) solution, Ka1 = 6.5 x 10-2 , Ka2 = 6.1 x 10-5
CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 11

Exercise 2.
1. How much NaOH (in grams) is needed to prepare 250 mL of solution with a pH of 10.00?

2. A solution is made by dissolving 18.25 g of HCl in 500 mL of water. Calculate the pH of the
solution. (Assume that the volume remains constant.)

3. A 0.040 M solution of a monoprotic acid is 10 percent ionized. Calculate the ionization constant
and pH of the acid.
CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 12

 Acid – base reaction


8.1. Neutralization reaction

acid + base 
 salt + H2O

molecular equation: HCl(aq) + NaOH(aq) 


 ……………. + …………….
(acid) (base) (salt) (water)

ionic equation: H+(aq) + Cl –(aq) + Na+(aq) + OH –(aq) 


 Na+(aq) + Cl –(aq) + H2O(l)

net ionic equation: ……………. + ……………. 


 …………….

EXAMPLE:

HNO3(aq) + KOH(aq) 
 ……………. + …………….

HCN(aq) + NaOH(aq) 
 NaCN(aq) + H2O(l)

2NaOH(aq) + H2SO4(aq) 
 ……………. + …………….

Ca(OH)2(s) + HCl(aq) 
 ……………. + …………….

Ba(OH)2(aq) + CH3COOH(aq) 
 ……………. + …………….

NaOH(aq) + CH3COOH(aq) 
 ……………. + …………….

H2CO3(aq) + Ca(OH)2(s) 
 ……………. + …………….

H3PO3(aq) + 3KOH(aq) 
 K3PO3(aq) + 3H2O(l)

HNO3(aq) + NH3(aq) 
 …………….

2NH3(aq) + H2SO4(aq) 
 (NH4)2SO4(aq)

8.2 Neutralization reaction leading to gas formation

- -
Certain salts like carbonates (containing the O ion), bicarbonates (containing the O ion),
-
sulfites (containing the O ion) and sulfides (containing the S2- ion) react with acids to form gaseous
products.

Na2CO3(aq) + 2HCl(aq) 
 ……………. + …………….

Carbonic acid is unstable and if present in solution in sufficient concentrations decomposes as


follows: ……………. 
 ……………. + …………….

EXAMPLE:

NaHCO3(aq) + HCl(aq) 
 ……………. + ……………. + …………….

Na2SO3(aq) + 2HCl(aq) 
 ……………. + ……………. + …………….

K2S(aq) + 2HCl(aq) 
 ……………. + ……………. + …………….
CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 13

8.3 Oxidation reaction of metals by acids and salts

Pattern: A + BX 
 AX + B (displacement reaction)

metal + acid 
 salt + H2

Mg(s) + 2HCl 
 ……………. + …………….

Zn(s) + 2HBr 
 ZnBr2(aq) + H2(g)

8.4 Oxides and hydroxides with formation of acid and base

 The basic metallic oxides react with water to form metal hydroxides:

HO
Na2O(s) 

2
2NaOH(aq)

BaO(s) H
2O
 Ba(OH)2(aq)

 Acidic oxides react with water to form acids:

CO2(g) + H2O(l) H2CO3(aq)

SO2(g) + H2O(l) H2SO3(aq)

SO3(g) + H2O(l) H2SO4(aq)

N2O5(g) + H2O(l) 2HNO3(aq)

P4O10(g) + 6H2O(l) 4H3PO4(aq)

Cl2O7(l) + H2O(l) 2HClO4(aq)

8.5 Acidic oxides and basic oxides react with acid and base to form salts

CO2(g) + 2NaOH(aq) 
 Na2CO3(aq) + H2O(l)

BaO(s) + 2HNO3(aq) 
 Ba(NO3)2(aq) + H2O(l)
Amphoteric

Al2O3(s) + 6HCl(aq) 
 2AlCl3(aq) + 3H2O(l)

Al2O3(s) + 2NaOH(aq) 
 2NaAlO2(aq) + H2O(l)

8.6 Basic and amphoteric hydroxides

For example: Al(OH)3, Be(OH)2

Al(OH)3(s) + 3HCl(aq) 
 AlCl3(aq) + 3H2O(l)

-
Al(OH)3(s) + OH –(aq) 
 O (a )

Be(OH)2 + 2HCl(aq) 
 BeCl2(aq) + 2H2O(l)

-
Be(OH)2 + 2OH –(aq) 
 eO (a )
CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 14

Acid – base properties of Salts


salt is an ionic compound formed by the reaction between an acid and a base. Salts are strong
electrolytes that completely dissociate into ions in water.
dissociate 100%
NaCl(s) 
 K+(aq) + Cl–(aq)

salt hydrolysis is the reaction of an anion or a cation of a salt, or both, with water.

Salt hydrolysis usually affects the pH of a solution:

1.) Neutral solution(pH = 7): strong base (cation) + strong acid (anion)

HO -
NaNO3(s) 

2
Na+(aq) + NO (aq) (not hydrolysis)

HO
KCl(s) 

2
K+(aq) + Cl–(aq) (not hydrolysis)

2.) Base solution(pH>7): strong base (cation) + weak acid (anion)


…………………………………… can hydro yzed

HO
CH3COONa(s) 

2
……………. + …………….

……………. + ……………. ……………. + …………….

[CH3 COO- ]hydrolyzed


pencent hydrolysis  100%
[CH3 COO- ]intial

3.) Acid solution(pH<7): weak base (cation) + strong acid(anion)


…………………………………… can hydro yzed

HO
NH4Cl(s) 

2
……………. + …………….

……………. + ……………. ……………. + …………….

or simply ……………. ……………. + …………….

EXAMPLE 1. Predict whether the following solutions will be acidic, basic, or nearly neutral:

(a.) NaNO2 =…………………….. (e.) CH3 OOLi =…………………….


(b.) KClO4 =…………………….. (f.) CH3NH3Br =……………………..
(c.) Na3PO4 =…………………….. (g.) NH4I =……………………..
(d.) KNO3 =…………………….. (h.) NaF =……………………..
CHEMISTRY: Acid – Base , Mr. Kiattisak Thaveekham, Lecturer. Kru Aum. 15

EXAMPLE 2. Calculate the pH and %hydrolysis of a 0.20 M sodium acetate solution, Ka= 1.8 x 10-5

Reference:

Brown, Theodore, et al. (2012). Chemistry: The central science, 12th ed. Boston: Prentice Hall.

Chang, Raymond. (2010). Chemistry, 10th ed. New York: McGraw Hill.

Oxtoby, David W., et al. (2012). Principles of modern chemistry, 6th ed. Belmont, CA: Thomson
Brooks/Cole.

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