KIMIA UNTUK TEKNIK SIPIL

3 SKS – Semester 1 (Wajib)

DEPARTEMEN TEKNIK SIPIL DAN LINGKUNGAN – FT UGM

Dr. Budi Kamulyan (A)

Dr. Sri Puji Saraswati (B)
Johan Syafri Mahathir Ahmad, Ph.D (C)
Rencana Perkuliahan

8. Reaksi Kimia & Kesetimbangan Kimia

9. Asam-Basa & Netralisasi
10.Reduksi-Oksidasi & Elektrolisis
ASAM – BASA
Models for Acid & Base

Models Definition of acid Definition of base

Arrhenius H+ (H3O+) producer OH- producer
Brnsted-Lowry Proton donor Proton acceptor
Lewis Electron-pair acceptor Electron-pair donor
Arrhenius Acid

Asam : produce H+ (H3O+) in solution

Basa : produce OH- in solution
Brnsted-Lowry

Asam : proton donor

Basa : proton acceptor

base acid acid base

conjugate conjugate
base acid
acid base
Conjugate Acids and Bases

• The term conjugate comes from the Latin word “conjugare,”

meaning “to join together.”
• Reactions between acids and bases always yield their conjugate
bases and acids.
Lewis

Asam : electron-pair acceptor

Basa : electron-pair donor
Examples of Conjugate Acid-Base Pairs

HNO3 – NO3-
H2SO4 – HSO4-
H3O+ – H2O
HF – F-
H3PO4 – H2PO4-
CH3COOH – CH3COO-
H2PO4- – HPO42-
NH4+ – NH3
H2O – OH-
#exercise

For each reaction, determine the acid and base:

1. Ni2+ + 6 NH3 → Ni(NH3)62+
2. H+ + H2O ⇄ H3O+
#exercise : Conjugate Acids & Bases

Write the formulas of the conjugate bases for the following acids:
H2CO3
HSO4-
Al(H2O)63+
Cr(OH)3(H2O)3
NH3
CO32-
C5H5N
Al(OH)3(H2O)3
Acid Strength and Ionization Constants

For the ionization or dissociation equilibrium of an acid in aqueous

solution, such as:

HA(aq) + H2O  H3O+(aq) + A-(aq);

The ionization or dissociation constant is expressed as follows:

[H 3O  ][A - ]
Ka 
[HA]

The values of Ka indicate the relative strength of the acids. Strong

acids have very large Ka, while weak acids have small Ka’s (Ka << 1)
Acid-Base Properties of Water

• Auto-ionization of water:

2H2O  H3O+(aq) + OH-(aq)

Kw = [H3O+][OH-] = 1.0 x 10-14 at 25oC

• Water ionizes to produce both H3O+ and OH-, thus it has both
acid and base properties. Kw is called water ionization constant.
• Pure water at 25oC: [H3O+] = [OH-] = 1.0 x 10-7 M
Acid-Base Properties of Water

Solution Is
[H+] = [OH-] neutral
At 250C [H+] > [OH-] acidic
Kw = [H+][OH-] = 1.0 x 10-14
[H+] < [OH-] basic
#exercise

Calculate [H+] or [OH-] as required for each of the following

solutions at 25°C, and state whether the solution is neutral, acidic, or
basic.
1. 1.0 x 10-5 M OH
2. 1.0 x 10-7 M OH
3. 10.0 M H
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+]
pH, pOH, pKw, Kw
• pH = -log[H+] (note: [H+] = [H3O+])

• pOH = -log[OH-]

• pKw = -log(Kw); pKa = -log(Ka); pKb = -log(Kb)

• For water, Kw = [H3O+][OH-] = 1.0 x 10-14

• -log(Kw) = -log [H3O+] + (-log[OH-])

• pKw = pH + pOH = 14.00

• At 25oC, pOH = 14 – pH
#exercise

The pH of rainwater collected in a northern part of

Sleman Region 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

Strong and Weak Acids

• Strong acids ionize completely in aqueous solution:

• HCl(aq) + H2O  H3O+(aq) + Cl-(aq);
• H2SO4(aq) + H2O  H3O+(aq) + HSO4-(aq);

• Weak acids ionize only partially in aqueous solution:

• HF(aq) + H2O ⇌ H3O+(aq) + F-(aq);
• HOCl(aq) + H2O ⇌ H3O+(aq) + ClO-(aq).
[H3O+] and pH of Strong Acids

• Strong acids like HCl and HClO4 ionize completely in aqueous

solution:

HCl(aq) + H2O  H3O+(aq) + Cl-(aq);

HClO4(aq) + H2O  H3O+(aq) + ClO4-(aq);

• In solutions of strong monoprotic acids HA, such as HCl and HClO4,

[H3O+] = [HA]0

• For example, in 0.10 M HCl, [H3O+] = 0.10 M, and pH = -log(0.10) =

1.00
[OH-] and pH of Strong Bases

• Like strong acids, strong bases also ionize completely in aqueous

solution.
• Examples: NaOH(aq)  Na+(aq) + OH-(aq);
Ba(OH)2(aq)  Ba2+(aq) + 2 OH-(aq);

• In a base solution such as 0.050 M NaOH,

[OH-] = [NaOH]0 = 0.050 M;
pOH = -log(0.050 M) = 1.30; pH = 14.00 - 1.30 = 12.70
• In a base solution such as 0.050 M Ba(OH)2,
[OH-] = 2 x [Ba(OH)2]0 = 0.10 M;
pOH = -log(0.10) = 1.00; pH = 14.00 - 1.00 = 13.00
[H3O+] and pH of Weak Acids

• Weak acids ionize only partially in aqueous solution

• In weak acid solutions, [H3O+] < [HA]0;
• [H3O+] and pH can be calculated from the initial concentration of
the acid and its Ka value (using chemical equilibrium concept).
#exercise

In 0.100 M acetic acid, CH3COOH, with Ka = 1.8 x 10-5, calculate

[H3O+] and pH!

(answer: [H3O+] = 1.34 x 10-3 M: pH = 2.873)

The pH of a mixture of weak acids
Calculate the pH of a solution that contains 1.00 M HCN (Ka = 6.2x10-10) and 5.00 M
HNO2 (Ka = 4.0x10-4). Also calculate the concentration of cyanide ion (CN ) in this
solution at equilibrium.

Solution
Since HCN and HNO2 are both weak acids and are largely undissociated, the major
species in the solution are: HCN, HNO2 and H2O.

Stronger acid

Predominant producer of H+
Percent Ionization

Remember: weak acids ionize only partially in aqueous solution.

[HA]ionized x
% Ionization   100%  x 100
[HA]initial (0.100 - x )

Example: We calculated that, in 0.10 M CH3COOH, the concentration of

acid that ionizes is 1.34 x 10-3 M. The percent ionization of 0.10 M
acetic acid:

1.34 x 10 -3 M
% ionization ~ x 100%  1.34%
0.100
The more we dilute the acid solution, the higher the fraction of
the acid that will ionize, which increases the degree of ionization
example

• At [CH3COOH]initial = 0.00100 M,
• [CH3COOH]ionized = 1.34 x 10-4 M (by approximation)

• At [CH3COOH]initial = 0.01000 M,
• [CH3COOH]ionized = 4.24 x 10-4 M (by approximation)
Exercise #3: pH and Percent Ionization

1) Nitrous acid, HNO2, has Ka = 4.0 x 10-4 at 25 oC. Calculate the pH

and percent ionization of HNO2 in 0.10 M solution of the acid.
(Answer: pH = 2.20; % ionization = 6.3%)

2) Chlorous acid, HOCl, has Ka = 3.5 x 10-8 at 25 oC. Calculate the

pH and percent ionization of HOCl in 0.10 M solution of the
acid.
(Answer: pH = 4.23; % ionization = 0.059%)
[OH-] and pH of Weak Bases

• Weak acids ionize only partially in aqueous solution

• In weak acid solutions, [H3O+] < [HA]0;
• [OH-] and pH can be calculated from the initial concentration of
the acid and its Kb value (using chemical equilibrium concept).
#exercise

in 0.100 M ammonia, NH3, with Kb = 1.8 x 10-5, calculate [OH-] and

pH!

(answer: [OH-] = 1.34 x 10-3 M: pH = 11.127)

Exercise #4: pH of Strong and Weak Bases

1) Ethylamine, C2H5NH, has Kb = 5.6 x 10-4. Calculate the

concentration of H3O+ in 0.10 M ethylamine solution and the pH
of the solution?
(Answer: [H3O+] = 1.3 x 10-12 M; pH = 11.87)

2) Pyridine, C5H5N, has Kb = 1.7 x 10-9. Calculate the concentration

of H3O+ in 0.020 M pyridine solution and the pH of the solution?
(Answer: [H3O+] = 1.7 x 10-9 M; pH = 8.77)
Polyprotic Acids

• Acids with more than one ionizable hydrogen ion, such as H2SO3,
H2SO4, H3PO4, H3C6H5O7, etc.

• Their hydrogen ionizes in stages, for example,

H3PO4(aq) + H2O ⇄ H3O+(aq) + H2PO4-(aq); Ka1 = 7.5 x 10-3
H2PO4-(aq) + H2O ⇄ H3O+(aq) + HPO42-(aq); Ka2 = 6.2 x 10-8
HPO42-(aq) + H2O ⇄ H3O+(aq) + PO43-(aq); Ka3 = 4.8 x 10-13

Acid strength decreases in the order:

H3PO4 >> H2PO4- >> HPO42-;
pH of solution is determined mainly by ionization of H3PO4
#example

Calculate the pH of a 5.0 M H3PO4 solution and the equilibrium

concentrations of the species H3PO4, H2PO4-, HPO42-, and PO43-.
The major species in solution are H3PO4 and H2O.
Polyprotic Acids: Sulfuric Acid

Sulfuric acid is unique among the common acids in that it is a strong

acid in its first dissociation and a weak acid in the second step

H2SO4 → H3O+ + HSO4- Ka1 = very large

HSO4- + H2O ⇄ H3O+ + SO42- Ka2 = 1.2 x 10-2

The dominant equilibrium is dissociation of H2SO4

Predominant producer of H3O+ is from H2SO4 dissociation

Example: Calculate the pH of a 1.0 M H2SO4 solution.

Acid-Base Properties of Salt Solutions

Soluble salts dissociate completely when dissolved in water;

Ions produced may react with water that release H3O+ and makes
the solution acidic, or produces OH- and makes the solution basic.

The acid-base property of a salt solution depends on whether the

compound is a product of:
Strong acid-strong base reaction: produces neutral salt
Strong acid-weak base reaction: produces acidic salt
Strong base-weak acid reaction: produces basic salt
Weak acid-weak base reaction: produces salt that is either
acidic or basic, depending on the relative strength of the
acid and the base.
Salts of Weak Acid-Weak Base
Reactions
• Salts produced by reactions of weak acids and weak bases can be
neutral, acidic, or basic, depending on the relative magnitude of
the Ka of the weak acid and the Kb of the weak base.

• If Ka ~ Kb, salts are neutral; example: NH4C2H3O2

• If Ka > Kb, salts are acidic; example: NH4NO2
• If Ka < Kb, salts are basic; example: NaC2H3O2
Predicting Acid-Base Property of Salts

Consider a solution containing NH4C2H3O2

NH4C2H3O2(aq)  NH4+(aq) + C2H3O2-(aq);

NH4+(aq) + H2O  H3O+(aq) + NH3(aq); Ka = 5.6 x 10-10

C2H3O2-(aq) + H2O  HC2H3O2(aq) + OH-(aq); Kb = 5.6 x 10-10

Ka = Kb = 5.6 x 10-10,  NH4C2H3O2 is neutral

Predicting Acid-Base Property of Salts

• Consider a solution containing (NH4)2SO4

• (NH4)2SO4(aq)  2NH4+(aq) + SO42-(aq);

• NH4+(aq) + H2O  H3O+(aq) + NH3(aq); Ka = 5.6 x 10-10

• SO42-(aq) + H2O  HSO4-(aq) + OH-(aq); Kb = 8.3 x 10-13

• Ka > Kb  (NH4)2SO4 is acidic;

Predicting Acid-Base Characteristics of Salts

• Now consider a solution containing NH4CN.

• NH4CN(aq)  NH4+(aq) + CN-(aq);

• NH4+(aq) + H2O  H3O+(aq) + NH3(aq); Ka = 5.6 x 10-10

• CN-(aq) + H2O  HCN(aq) + OH-(aq); Kb = 1.6 x 10-5

• Kb > Ka  NH4CN is basic

Effect of Structure on Acid-Base Properties

• Relative bond strength:

H─F > H─Cl > H─Br > H─I

• Relative acid strength:

HI > HBr > HCl > HF
• (HF is the only weak acid in this group)

• Relative acid strength:

H2Te > H2Se > H2S > H2O (all very weak acids)
Effect of Structure on Acid-Base Properties

Electronegativity Effect on Relative Strength of Oxo-Acids:

Same central atom, but different numbers of oxygen atoms:
HOClO3 > HOClO2 > HOClO > HOCl;

Same number of oxygen, but different central atoms:

Trend of electronegativity: F > Cl > Br > I;
Trend of relative acidity: HOF > HClO > HOBr > HOI;
Relative acidity: CF3COOH > CCl3COOH > CH3COOH
Trend of electronegativity: Cl > S > P > Si
Relative acidity: HClO4 > H2SO4 > H3PO4 > H4SiO4
Factors Affecting Acid Strength

• The more polar the H–X bond

and/or the weaker the H–X
bond, the more acidic the
compound.
• So acidity increases from left
to right across a row and from
top to bottom down a group.
NEUTRALIZATION
Principle

Acid + Base ⇄ Salt + Water

HA + BOH ⇄ BA + H2O

In a neutralization reaction
• an acid such as HCl reacts with a base such as NaOH.
HCl + H2O ⇄ H3O+ + Cl−
NaOH ⇄ Na+ + OH−

• the H3O+ from the acid and the OH− from the base form water.
H3O+ + OH− ⇄ 2 H2O
What is the molarity of an HCl solution if 18.5 mL of a
0.225 M NaOH are required to neutralize 10.0 mL HCl?

Step 1.
Reaction = HCl(aq) + NaOH(aq) ⟶ NaCl(aq) + H2O(l)

Step 2.
Mol of acid = mol of base
M a x Va = M b x Vb
Ma (M) x 0.01 (L) = 0.225 (M) x 0.0185 (L)
Ma (M) = 0.416 M
Calculate the pH of the resulting solution when 200
mL of a 0.15 M solution of HBr is mixed with 100 mL
of a 0.2 M solution of KOH!
Step 1.
Reaction: HBr(aq) + KOH(aq) ⟶ KBr(aq) + H2O(l)

Step 2. Initial mol of each substance

HBr = 0.2 L x 0.15 M = 0.03 mol
KOH = 0.1 L x 0.20 M = 0.02 mol
Total volume = 0.2 L + 0.1 L = 0.3 L

Step 3. Equilibrium

HBr KOH KBr

Initial (mol) 0.03 0.02
Reaction 0.02 0.02
Step 3. Equilibrium

HBr KOH KBr

Initial (mol) 0.03 0.02
Reaction 0.02 0.02 0.02
Equilibrium 0.01 - 0.02

Step 4
Excess HBr will cause further dissociation
HBr + H2O ⟶ H3O+ + Br-

[H3O+] = [HBr]excess
= 0.01 (mol) / 0.3 (L)
= 0.3 X 10-2 M

pH = - log [H3O+]
= - log 0.3 X 10-2
= 1.48