Asam dan Basa

&
Kesetimbangan Asam dan Basa
Acids and Bases
 Acids

Have a sour taste. Vinegar owes its taste to acetic acid. Citrus
fruits contain citric acid.

React with certain metals to produce hydrogen gas.

React with carbonates and bicarbonates to produce carbon

dioxide gas

Bases
Have a bitter taste.

Feel slippery. Many soaps contain bases.

4.3
Arrhenius acid is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water

4.3
 A Brnsted acid is a proton donor
A Brnsted base is a proton acceptor

base acid acid base

conjugate acid conjugate base

base acid

15.1
 Acid-Base Properties of Water

H2O (l) H+ (aq) + OH- (aq)

autoionization of water

+ -
H O + H O
[ H O H
] + H O

H H H

conjugate acid
base

H2O + H2O H3O+ + OH-

acid conjugate base
15.2
 The Ion Product of Water
[H+][OH-]
H2O (l) H+ (aq) + OH- (aq) Kc = [H2O] = constant
[H2O]

Kc[H2O] = Kw = [H+][OH-]

The ion-product constant (Kw) is the product of the molar concentrations of H+ and OH- ions
at a particular temperature.

Solution Is

[H+] = [OH-] neutral

At 250C
[H+] > [OH-] acidic
Kw = [H+][OH-] = 1.0 x 10-14
[H+] < [OH-] basic

15.2
What is the concentration of OH- ions in a HCl solution whose hydrogen ion
concentration is 1.3 M?

Kw = [H+][OH-] = 1.0 x 10-14

[H+] = 1.3 M

Kw 1 x 10-14
[OH-] = = = 7.7 x 10-15 M
[H+] 1.3

15.2
 pH A Measure of Acidity

pH = -log [H+]

Solution Is At 250C

neutral [H+] = [OH-] [H+] = 1 x 10-7 pH = 7

acidic [H+] > [OH-] [H+] > 1 x 10-7 pH < 7

basic [H+] < [OH-] [H+] < 1 x 10-7 pH > 7

pH [H+]

15.3
 pOH = -log [OH-]

[H+][OH-] = Kw = 1.0 x 10-14

-log [H+] log [OH-] = 14.00

pH + pOH = 14.00

15.3
The pH of rainwater collected in a certain region of the northeastern United States on
a particular day was 4.82. What is the H+ ion concentration of the rainwater?

pH = -log [H+]

[H+] = 10-pH = 10-4.82 = 1.5 x 10-5 M

The OH- ion concentration of a blood sample is 2.5 x 10-7 M. What is the pH of the
blood?

pH + pOH = 14.00

pOH = -log [OH-] = -log (2.5 x 10-7) = 6.60

pH = 14.00 pOH = 14.00 6.60 = 7.40

15.3
 Strong Electrolyte 100% dissociation
H2O
NaCl (s) Na+ (aq) + Cl- (aq)

Weak Electrolyte not completely dissociated

CH3COOH CH3COO- (aq) + H+ (aq)

Strong Acids are strong electrolytes

HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)

HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)

HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4- (aq)

H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq)

15.4
Weak Acids are weak electrolytes

HF (aq) + H2O (l) H3O+ (aq) + F- (aq)

HNO2 (aq) + H2O (l) H3O+ (aq) + NO2- (aq)

HSO4- (aq) + H2O (l) H3O+ (aq) + SO42- (aq)

H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)

Strong Bases are strong electrolytes

H2O
NaOH (s) Na+ (aq) + OH- (aq)
H2O
KOH (s) K+ (aq) + OH- (aq)
H2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)

15.4
Weak Bases are weak electrolytes

F- (aq) + H2O (l) OH- (aq) + HF (aq)

NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

Conjugate acid-base pairs:

The conjugate base of a strong acid has no measurable
strength.
H3O+ is the strongest acid that can exist in aqueous
solution.
The OH- ion is the strongest base that can exist in aqeous
solution.

15.4
15.4
Strong Acid Weak Acid

15.4
 What is the pH of a 2 x 10-3 M HNO3 solution?

HNO3 is a strong acid 100% dissociation.

Start 0.002 M 0.0 M 0.0 M

HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
End 0.0 M 0.002 M 0.002 M

pH = -log [H+] = -log [H3O+] = -log(0.002) = 2.7

What is the pH of a 1.8 x 10-2 M Ba(OH)2 solution?

Ba(OH)2 is a strong base 100% dissociation.

Start 0.018 M 0.0 M 0.0 M

Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)
End 0.0 M 0.018 M 0.036 M

pH = 14.00 pOH = 14.00 + log(0.036) = 12.6

15.4
Weak Acids (HA) and Acid Ionization Constants
HA (aq) + H2O (l) H3O+ (aq) + A- (aq)

HA (aq) H+ (aq) + A- (aq)

[H+][A-]
Ka =
[HA]

Ka is the acid ionization constant

weak acid
Ka strength

15.5
15.5
 What is the pH of a 0.5 M HF solution (at 250C)?
[H+][F-]
HF (aq) H+ (aq) + F- (aq) Ka = = 7.1 x 10-4
[HF]

HF (aq) H+ (aq) + F- (aq)

Initial (M) 0.50 0.00 0.00

Change (M) -x +x +x

Equilibrium (M) 0.50 - x x x

x2
Ka = = 7.1 x 10-4 Ka << 1 0.50 x 0.50
0.50 - x

x2
Ka = 7.1 x 10-4 x2 = 3.55 x 10-4 x = 0.019 M
0.50

[H+] = [F-] = 0.019 M pH = -log [H+] = 1.72

[HF] = 0.50 x = 0.48 M

15.5
 When can I use the approximation?

Ka << 1 0.50 x 0.50

When x is less than 5% of the value from which it is subtracted.

0.019 M Less than 5%

x = 0.019 x 100% = 3.8% Approximation ok.
0.50 M

What is the pH of a 0.05 M HF solution (at 250C)?

x2
Ka = 7.1 x 10-4 x = 0.006 M
0.05

0.006 M More than 5%

x 100% = 12%
0.05 M Approximation not ok.

Must solve for x exactly using quadratic equation or method of successive approximation.

15.5
Solving weak acid ionization problems:
1. Identify the major species that can affect the pH.
In most cases, you can ignore the autoionization of
water.
Ignore [OH-] because it is determined by [H+].
2. Use ICE to express the equilibrium concentrations in terms
of single unknown x.
3. Write Ka in terms of equilibrium concentrations. Solve for x
by the approximation method. If approximation is not valid,
solve for x exactly.
4. Calculate concentrations of all species and/or pH of the
solution.

15.5
 What is the pH of a 0.122 M monoprotic acid whose
Ka is 5.7 x 10-4?

HA (aq) H+ (aq) + A- (aq)

Initial (M) 0.122 0.00 0.00

Change (M) -x +x +x

Equilibrium (M) 0.122 - x x x

x2
Ka = = 5.7 x 10-4 Ka << 1 0.122 x 0.122
0.122 - x

x2
Ka = 5.7 x 10-4 x2 = 6.95 x 10-5 x = 0.0083 M
0.122

0.0083 M More than 5%

x 100% = 6.8% Approximation not ok.
0.122 M

15.5
 x2
Ka = = 5.7 x 10-4 x2 + 0.00057x 6.95 x 10-5 = 0
0.122 - x

ax2 + bx + c =0 x=

-b b2 4ac
2a

x = 0.0081 x = - 0.0081

HA (aq) H+ (aq) + A- (aq)

Initial (M) 0.122 0.00 0.00

Change (M) -x +x +x

Equilibrium (M) 0.122 - x x x

[H+] = x = 0.0081 M pH = -log[H+] = 2.09

15.5
percent ionization =
Ionized acid concentration at equilibrium x 100%
Initial concentration of acid

For a monoprotic acid HA

[H+]
Percent ionization = x 100% [HA]0 = initial concentration
[HA]0

15.5
Weak Bases and Base Ionization Constants
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

[NH4+][OH-]
Kb =
[NH3]

Kb is the base ionization constant

weak base
Kb strength

Solve weak base problems like weak acids except solve for [OH-]
instead of [H+].

15.6
15.6
Ionization Constants of Conjugate Acid-Base Pairs

HA (aq) H+ (aq) + A- (aq) Ka

A- (aq) + H2O (l) OH- (aq) + HA (aq) Kb

H2O (l) H+ (aq) + OH- (aq) Kw

KaKb = Kw

Weak Acid and Its Conjugate Base

Kw Kw
Ka = Kb =
Kb Ka

15.7
15.8
 Molecular Structure and Acid Strength
H X H+ + X-

The stronger the The weaker

bond the acid

HF << HCl < HBr < HI

15.9
 Molecular Structure and Acid Strength
d- d+
O O- + H
Z H Z +

The O-H bond will be more polar and easier to break if:
Z is very electronegative or
Z is in a high oxidation state

15.9
 Molecular Structure and Acid Strength

1. Oxoacids having different central atoms (Z) that are from the same group and that have
the same oxidation number.

Acid strength increases with increasing electronegativity of Z

O O

H O Cl O H O Br O

Cl is more electronegative than Br

HClO3 > HBrO3

15.9
 Molecular Structure and Acid Strength

2. Oxoacids having the same central atom (Z) but different numbers of attached groups.

Acid strength increases as the oxidation number of Z increases.

HClO4 > HClO3 > HClO2 > HClO

15.9
 Acid-Base Properties of Salts
Neutral Solutions:

Salts containing an alkali metal or alkaline earth metal ion (except Be2+) and the
conjugate base of a strong acid (e.g. Cl-, Br-, and NO3-).

H2O
NaCl (s) Na+ (aq) + Cl- (aq)

Basic Solutions:

Salts derived from a strong base and a weak acid.

NaCH3COOH (s) H2O+ CH COO- (aq)

Na+ (aq) 3

CH3COO- (aq) + H2O (l) CH3COOH (aq) + OH- (aq)

15.10
 Acid-Base Properties of Salts
Acid Solutions:

Salts derived from a strong acid and a weak base.

NH4Cl (s) H2O+ (aq) + Cl- (aq)

NH 4

NH4+ (aq) NH3 (aq) + H+ (aq)

Salts with small, highly charged metal cations (e.g. Al3+, Cr3+, and Be2+) and the
conjugate base of a strong acid.

3+
Al(H2O)6 (aq) Al(OH)(H2O)5 (aq) + H+ (aq)2+

15.10
Acid Hydrolysis of Al3+

15.10
 Acid-Base Properties of Salts
Solutions in which both the cation and the anion hydrolyze:

Kb for the anion > Ka for the cation, solution will be basic
Kb for the anion < Ka for the cation, solution will be acidic
Kb for the anion Ka for the cation, solution will be neutral

15.10
Oxides of the Representative Elements
In Their Highest Oxidation States

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

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

15.11
 Definition of An Acid
Arrhenius acid is a substance that produces H+ (H3O+) in water

A Brnsted acid is a proton donor

A Lewis acid is a substance that can accept a pair of electrons

A Lewis base is a substance that can donate a pair of electrons

H+ + OH- H O H

acid base

H H
+
H+ + N H H N H

H H
acid base
15.12
 Lewis Acids and Bases

F H F H

F B + N H F B N H

F H F H

acid base

No protons donated or accepted!

15.12
 Chemistry In Action: Antacids and the Stomach pH Balance

NaHCO3 (aq) + HCl (aq)

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

Mg(OH)2 (s) + 2HCl (aq)

MgCl2 (aq) + 2H2O (l)
Acid-Base Equilibria and
Solubility Equilibria
The common ion effect is the shift in equilibrium caused by the addition of a compound
having an ion in common with the dissolved substance.

The presence of a common ion suppresses the ionization of a

weak acid or a weak base.

Consider mixture of CH3COONa (strong electrolyte) and CH3COOH (weak acid).

CH3COONa (s) Na+ (aq) + CH3COO- (aq)

common
CH3COOH (aq) H+ (aq) + CH3COO- (aq) ion

16.2
 Consider mixture of salt NaA and weak acid HA.

NaA (s) Na+ (aq) + A- (aq)

[H+][A-]
Ka =
HA (aq) H+ (aq) + A- (aq) [HA]

Ka [HA]
[H+] =
[A-] Henderson-Hasselbalch equation

[HA]
-log [H+] = -log Ka - log
[A-]
[conjugate base]
pH = pKa + log
[A-] [acid]
-log [H+] = -log Ka + log
[HA]

[A-]
pH = pKa + log pKa = -log Ka
[HA]

16.2
 What is the pH of a solution containing 0.30 M HCOOH and 0.52 M HCOOK?

Mixture of weak acid and conjugate base!

HCOOH (aq) H+ (aq) + HCOO- (aq)

Initial (M) 0.30 0.00 0.52

Change (M) -x +x +x

Equilibrium (M) 0.30 - x x 0.52 + x

[HCOO-]
Common ion effect pH = pKa + log
[HCOOH]
0.30 x 0.30
[0.52]
0.52 + x 0.52 pH = 3.77 + log = 4.01
[0.30]

HCOOH pKa = 3.77

16.2
A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!
A buffer solution has the ability to resist changes in pH upon the addition of small
amounts of either acid or base.

Consider an equal molar mixture of CH3COOH and CH3COONa

Add strong acid

H+ (aq) + CH3COO- (aq) CH3COOH (aq)
Add strong base
OH- (aq) + CH3COOH (aq) CH3COO- (aq) + H2O (l)

16.3
 HCl H+ + Cl-

HCl + CH3COO- CH3COOH + Cl-

16.3
 Which of the following are buffer systems? (a) KF/HF
(b) KBr/HBr, (c) Na2CO3/NaHCO3

(a) KF is a weak acid and F- is its conjugate base

buffer solution

(b) HBr is a strong acid

not a buffer solution

(c) CO32- is a weak base and HCO3- is its conjugate acid

buffer solution

16.3
 Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer system. What is the pH after
the addition of 20.0 mL of 0.050 M NaOH to 80.0 mL of the buffer solution?

NH4+ (aq) H+ (aq) + NH3 (aq)

[NH3] [0.30]
pH = pKa + log pKa = 9.25 pH = 9.25 + log = 9.17
[NH4 +] [0.36]

start (moles) 0.029 0.001 0.024

NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)

end (moles) 0.028 0.0 0.025

final volume = 80.0 mL + 20.0 mL = 100 mL

0.028 0.025 [0.25]

+]
[NH4 = [NH3] = pH = 9.25 + log = 9.20
0.10 0.10 [0.28]
16.3
Chemistry In Action: Maintaining the pH of Blood

16.3
 Titrations
In a titration a solution of accurately known concentration is added gradually added to
another solution of unknown concentration until the chemical reaction between the two
solutions is complete.

Equivalence point the point at which the reaction is complete

Indicator substance that changes color at (or near) the

equivalence point

Slowly add base

to unknown acid
UNTIL

The indicator
changes color
(pink)
4.7
Strong Acid-Strong Base Titrations

NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)

OH- (aq) + H+ (aq) H2O (l)

16.4
Weak Acid-Strong Base Titrations

CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)

CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)

At equivalence point (pH > 7):

CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)

16.4
Strong Acid-Weak Base Titrations

HCl (aq) + NH3 (aq) NH4Cl (aq)

H+ (aq) + NH3 (aq) NH4Cl (aq)

At equivalence point (pH < 7):

NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)

16.4
 Exactly 100 mL of 0.10 M HNO2 are titrated with a 0.10 M NaOH solution. What is the
pH at the equivalence point ?

start (moles) 0.01 0.01

HNO2 (aq) + OH- (aq) NO2- (aq) + H2O (l)
end (moles) 0.0 0.0 0.01
0.01
Final volume = 200 mL [NO2-] = = 0.05 M
0.200
NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

Initial (M) 0.05 0.00 0.00

Change (M) -x +x +x

Equilibrium (M) 0.05 - x x x

[OH-][HNO2] x2
Kb = = = 2.2 x 10-11 pOH = 5.98
[NO2-] 0.05-x

0.05 x 0.05 x 1.05 x 10-6 = [OH-] pH = 14 pOH = 8.02

 Acid-Base Indicators
HIn (aq) H+ (aq) + In- (aq)
[HIn]
10 Color of acid (HIn) predominates
[In-]

[HIn]
10 Color of conjugate base (In-) predominates
[In-]

16.5
pH

16.5
The titration curve of a strong acid with a strong base.

16.5
 Which indicator(s) would you use for a titration of HNO2 with KOH ?

Weak acid titrated with strong base.

At equivalence point, will have conjugate base of weak acid.
At equivalence point, pH > 7
Use cresol red or phenolphthalein

16.5
 Solubility Equilibria

AgCl (s) Ag+ (aq) + Cl- (aq)

Ksp = [Ag+][Cl-] Ksp is the solubility product constant

MgF2 (s) Mg2+ (aq) + 2F- (aq) Ksp = [Mg2+][F-]2

Ag2CO3 (s) 2Ag+ (aq) + CO32- (aq) Ksp = [Ag+]2[CO32-]

Ca3(PO4)2 (s) 3Ca2+ (aq) + 2PO43- (aq) Ksp = [Ca2+]3[PO43-]2

Dissolution of an ionic solid in aqueous solution:

Q < Ksp Unsaturated solution No precipitate

Q = Ksp Saturated solution

Q > Ksp Supersaturated solution Precipitate will form

16.6
16.6
Molar solubility (mol/L) is the number of moles of solute dissolved in 1 L of a saturated
solution.

Solubility (g/L) is the number of grams of solute dissolved in 1 L of a saturated solution.

16.6
 What is the solubility of silver chloride in g/L ?

AgCl (s) Ag+ (aq) + Cl- (aq) Ksp = 1.6 x 10-10

Initial (M) 0.00 0.00 Ksp = [Ag+][Cl-]
Change (M) +s +s Ksp = s2

Equilibrium (M) s s
s = Ksp

s = 1.3 x 10-5
[Ag+] = 1.3 x 10-5 M [Cl-] = 1.3 x 10-5 M

1.3 x 10-5 mol AgCl 143.35 g AgCl

Solubility of AgCl = x = 1.9 x 10-3 g/L
1 L soln 1 mol AgCl

16.6
16.6
 If 2.00 mL of 0.200 M NaOH are added to 1.00 L of 0.100 M CaCl2, will a
precipitate form?

The ions present in solution are Na+, OH-, Ca2+, Cl-.

Only possible precipitate is Ca(OH)2 (solubility rules).

Is Q > Ksp for Ca(OH)2?

[Ca2+]0 = 0.100 M [OH-]0 = 4.0 x 10-4 M

Q = [Ca2+]0[OH-]0 2 = 0.10 x (4.0 x 10-4)2 = 1.6 x 10-8

Ksp = [Ca2+][OH-]2 = 8.0 x 10-6

Q < Ksp No precipitate will form

16.6
 What concentration of Ag is required to precipitate ONLY AgBr in a solution that
contains both Br- and Cl- at a concentration of 0.02 M?

AgBr (s) Ag+ (aq) + Br- (aq) Ksp = 7.7 x 10-13

K = [Ag+][Br-]
sp

Ksp 7.7 x 10-13

[Ag+] = = = 3.9 x 10-11 M
[Br-] 0.020

AgCl (s) Ag+ (aq) + Cl- (aq) Ksp = 1.6 x 10-10

Ksp = [Ag+][Cl-]
Ksp 1.6 x 10-10
[Ag+] = = = 8.0 x 10-9 M
[Cl-] 0.020

3.9 x 10-11 M < [Ag+] < 8.0 x 10-9 M

16.7
 The Common Ion Effect and Solubility

The presence of a common ion decreases the solubility of the

salt.

What is the molar solubility of AgBr in (a) pure water and (b) 0.0010 M NaBr?

NaBr (s) Na+ (aq) + Br- (aq)

AgBr (s) Ag+ (aq) + Br- (aq)
[Br-] = 0.0010 M
Ksp = 7.7 x 10-13
AgBr (s) Ag+ (aq) + Br- (aq)
s2 = Ksp
[Ag+] = s
s = 8.8 x 10-7
[Br-] = 0.0010 + s 0.0010
Ksp = 0.0010 x s

s = 7.7 x 10-10
16.8
 pH and Solubility

The presence of a common ion decreases the solubility.

Insoluble bases dissolve in acidic solutions
Insoluble acids dissolve in basic solutions
remove
add
Mg(OH)2 (s) Mg2+ (aq) + 2OH- (aq)

At pH less than 10.45

Ksp = [Mg2+][OH-]2 = 1.2 x 10-11
Lower [OH-]
Ksp = (s)(2s)2 = 4s3
OH- (aq) + H+ (aq) H2O (l)
4s3 = 1.2 x 10-11
Increase solubility of Mg(OH)2
s = 1.4 x 10-4 M
[OH-] = 2s = 2.8 x 10-4 M At pH greater than 10.45

pOH = 3.55 pH = 10.45 Raise [OH-]

Decrease solubility of Mg(OH)2

16.9
 Complex Ion Equilibria and Solubility
A complex ion is an ion containing a central metal cation bonded to one or more molecules
or ions.

Co2+ (aq) + 4Cl- (aq) CoCl4 (aq) 2-

The formation constant or stability constant (Kf) is the equilibrium constant for the
complex ion formation.

[CoCl4 2-
]
Kf =
2+ [Co2+][Cl-]4
Co(H2O)6 CoCl2-
4

stability of
Kf complex

16.10
16.10
16.11
Qualitative
Analysis of
Cations

16.11
 Flame Test for Cations

lithium sodium potassium copper

16.11
 Chemistry In Action: How an Eggshell is Formed

Ca2+ (aq) + CO32- (aq) CaCO3 (s)

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

H2CO3 (aq) H+ (aq) + HCO3- (aq)

HCO3- (aq) H+ (aq) + CO32- (aq)