ACIDS & BASES

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Acids and Bases: Arrhenius Definition
§ An acid is a substance that dissociates in water
to yield H3O+.
§ A base is a substance that dissociates in water
to yield OH–.
§ This explains why all neutralization reactions
between strong acids and bases and have
similar heats of reaction:
H+(aq) + OH–(aq) ® H2O(l) DH0 = -57 kJ/mol

2
 Acids and Bases: Arrhenius Definition
Arrhenius acid is a substance that produces H+ (H3O+) in water.

Arrhenius base is a substance that produces OH- in water.

Can something be an acid/base if its not soluble in water?

Brønsted and Lowry proposed a more general definition…
 Brønsted Acids
Bronsted Acids- able to donate a proton in the form of
hydrogen ions – protons – H+.

AH A - + H+
Typically :
• have a sour taste (vinegar-acetic acid, lemons-citric acid)

• change the color of litmus from blue to red.

• react with carbonates to produce CO2.

H3CCOOH(aq) + NaHCO3(s) NaOOCCH3(aq) + CO2(g) + H2O(l)
 Brønsted Bases
Bronsted Base- able to accept a proton in the form of
hydrogen ions – protons – H+.

B- + H+ BH
Typically :
• have a lone pair of electrons.

• have a bitter taste (antacids-Mg(OH2)).

• change the color of litmus from red to blue.

• feel slippery (turns your cells and fat into soap!).

 Brønsted Acid/Base
Bronsted Acids- able to donate a proton in the form
of hydrogen ions – protons – H+.

AH A- + H+

Bronsted Base- able to accept a proton in the form

of hydrogen ions – protons – H+. Typically has a
lone pair.

B- + H+ BH
 Acid-Base Neutralization
acid + base salt + water

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

H+ + Cl- + Na+ + OH- Na+ + Cl- + H2O

H+ + OH- H2O
 Acid-Base Neutralization
acid + base salt + water + CO2

2HCl (aq) + Na2CO3 (aq) 2NaCl (aq) + H2O +CO2

2H+ + 2Cl- + 2Na+ + CO32- 2Na+ + 2Cl- + H2O + CO2

2H+ + CO32- H2O + CO2
 Note on: Acids in Water
A strong acid like HCl will dissociate:
HCl à Cl- + H+
H+ does not freely exist in water.
In water:
hydronium ion ≈ hydrogen ion
H3O+ ≈ H+
[H+] is often used as an
abbreviation for [H3O+]. However,
H+ does not exist in water.

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 Bronsted Acid and Base
Bronsted Acids- able to donate protons in the form of
hydrogen ions – protons – H+.

AH A - + H+
HCl à Cl- + H+
C2H3O2H à C2H3O2- + H+

Bronsted Base- able to accept protons in the form

of hydrogen ions or H+.

B- + H+ BH
NH3 + H+ à NH4+

HO- + H+ à H 2O
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 Conjugate Acid-Base Pairs
§ Consider the ionization of HCl:
A Brønsted acid is a
HCl(g) + H2O(l) ¾® Cl–(aq) + H3O+(aq) proton donor
A Brønsted base is a
§ HCl donates a proton, thus it is an acid. proton acceptor
§ H2O accepts a proton and is a base.
§ Now, consider the reverse reaction:
HCl(g) + H2O(l) ¬¾ Cl–(aq) + H3O+(aq)
§ Cl– acts as a base because it accepts a proton from
H3O+, an acid.

§ Therefore, HCl is an acid, but after loosing a

proton, Cl– is a base.
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 Conjugate Acid-Base Pairs
HCl(g) + H2O(l) ¾® Cl–(aq) + H3O+(aq)
acid1 base2 base1 acid2
§ HCl and Cl– are a conjugate acid-base pair:
§ HCl is a conjugate acid of Cl–
§ Cl– is a conjugate base of HCl

§ H2O and H3O+ are also a conjugate acid-base pair.

§ In a Brønsted-Lowry acid-base reaction, an acid and a base

react to form their conjugate base and conjugate acid,
respectively.
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 Conjugate Acid-Base Pairs

In the reaction of HF and H2O,

• HF/F− is one conjugate acid-base pair.
• H2O/H3O+ is the other conjugate acid-base pair.
• Each pair is related by a loss and gain of H+.
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 Conjugate Acid-Base Pairs

In the reaction of NH3 and H2O,

• one conjugate acid-base pair is NH3/NH4+
• the other conjugate acid-base is H2O/H3O+.

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What is the conjugate base of:
H2 S NH4+ H2CO3
A) HS A) NH3- A) HCO3-
B) HS+ B) NH3 B) CO2
C) S2- C) NH3+ C) CO32-
D) HS- D) NH2- D) HCO22-

AH A - + H+
AH+ A + H+
AH- A2- + H+
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Question:
What is the conjugate acid of:
NO2- NH2- OH-
A) HNO2+ A) NH2 A) H2O+
B) HNO2 B) NH2- B) H2O-
C) HNO2 - C) NH2+ C) H3O+
D) HNO22+ D) NH3+ D) H2O

B- + H+ BH
B + H+ BH+
B+ + H+ BH2+
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 Conjugate Acid-Base Pairs
§ Identify conjugate acid-base pairs in the following
reactions:
NH4+ + H2O ¾® NH3 + H3O+

H2S + NH3 ¾® HS– + NH4+

H3PO4 + H2O ¾® H2PO4– + H3O+

H2O + HS– ¾® HO- + H2S

Water acts as an acid and a base!

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 Amphiprotic Species
Amphiprotic or amphoteric- species that can gain or
lose a proton under the appropriate conditions

Acid Base

Base Acid

Water acts as an acid and a base!

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 Water Acid-Base Reaction
+ + H -
H O + H O [ H O H ] O
H H H

acid base conjugate conjugate

acid base

H2O + H2O H3O+ + OH- H 3 O + ≈ H+

H2O(l) H+(aq) + OH-(aq)
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 Autoionization of Water
§ Even very pure water exhibits a very small residual
conductance. Water is a very weak electrolyte.
§ The dissociation of a pure liquid is known as
autoionization (or self-ionization).
§ The dissociation is reversible.
H2O(l) H+(aq) + OH-(aq)

Kw = [H+][OH-]
Kw is called the ion-product constant of water.
At 250C
Kw = [H+][OH-] = 1.0 x 10-14 20
 Acidic, Basic, and Neutral Solutions
Kw = [H+][OH-] = 1.0 x 10-14
§ In a neutral solution
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[H ] [OH ] 1.0 10 1.0 10 7 M

§ In an acidic solution
[H] 1.0 10 7 M; [OH ] 1.0 10 7 M

§ In a basic solution
[H ] 1.0 10 7 M; [OH ] 1.0 10 7 M

§ Note that at all times [H+] = [OH-] neutral

[H ][OH ] Kw 1.0 10 14 [H+] > [OH-] acidic
[H+] < [OH-] basic
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Example

The concentration of OH- ions in a certain household ammonia

cleaning solution is 0.0025 M. Calculate the concentration of
H+ ions. Is the solution acidic or basic?

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

[OH-] = 0.0025 M
-14
+ K w 1.0 × 10 -12
[H ] = -
= = 4.0 × 10 M
[OH ] 0.0025

[H+] < [OH-]

The solution is basic. But how basic? 22
 pH Scale

pH = -log [H+]

Solution Is At 250C
neutral [H+] = [OH-] [H+] = 1.0 x 10-7 pH = 7
acidic [H+] > [OH-] [H+] > 1.0 x 10-7 pH < 7
basic [H+] < [OH-] [H+] < 1.0 x 10-7 pH > 7

pH [H+]

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pH = -log [H+]

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 pOH Scale
§ In the analogy to the pH scale, we can define a
pOH-scale for the concentration [OH–].
Kw = [H+][OH-] = 1.0 x 10-14

-log [H+] – log [OH-] = 14 pOH = -log [OH-]

pH + pOH = 14

§ It is important to remember that:

This relation is valid only at 25°C!
At other temperatures, the autoionization constant
of water and, therefore, the (pH+pOH) are different.
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 Relevant Equations Summary
1) Kw = [H+][OH-] = 1.0 x 10-14

2) pH = -log [H+]

3) pOH = -log [OH]

4) pH + pOH = 14
If you know [H+],
you can calculate pH using equation 2.
you can calculate [OH-] using equation 1 (or 2+4+3)
you can calculate pOH using equation 1+3 (or 2+4)
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Example
The concentration of H+ ions in a bottle of liquid was
3.2 x 10-4 M right after the cork was removed. Only half of the
liquid was consumed. The other half, after it had been standing
open to the air for a month, was found to have a hydrogen ion
concentration equal to 1.0 x 10-3 M. Calculate the pH of the
liquid on these two occasions.
pH = -log [H+]
At time 0:
[H+] = 3.2 x 10-4 M
pH = -log (3.2 x 10-4) = 3.49
At time 1 month:
[H+] = 1.0 x 10-3 M
pH = -log (1.0 x 10-3 ) = 3.00
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Example
The pH of rainwater collected in a certain region of the
northeastern United States on a particular day was 4.82.
Calculate the H+ ion concentration of the rainwater.

pH = -log [H+] What is the

pOH?
4.82 = -log [H+]

-4.82 = log [H+]

10-4.82 = 10log [H+]

1.5 x 10-5 M = [H+]

Experimental values are almost always

reported in pH, not pOH! 28
Why we use pH and not pOH

pH Meter

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 Strong and Weak Acids
• Acids can be either strong electrolytes or weak electrolytes.
• Strong acids completely break up into their ions:
HCl (aq) à H+(aq) + Cl-(aq)

• Weak acids only partially break up into their ions:

HC2H3O2 ó H+ (aq) + C2H3O2-(aq)
Weak acids don’t completely dissociate, they go to equilibrium!

§ The extent of dissociation has a dramatic effect on the reactivity of

acids.

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 Strong and Weak Acids
§ 6 Strong acids:
§ The hydrohalic acids (HCl, HBr, and HI).
§ Oxoacids in which the number of O atoms exceeds
the number of ionizable protons by two or more,
for example, HNO3, H2SO4, HClO4.
§ Weak acids:
§ Any H+ donor that is not those six.
§ Hydrofluoric acid (HF).
§ Oxoacids in which the number of O atoms equals
or exceeds by one the number of ionizable
protons, for example, HNO2, H2SO3, H4SiO4.
§ Acids in which H is not bonded to O or halogen,
such as H2S, HCN.
§ Carboxylic acids, such as CH3COOH, C6H5COOH. 31
 Strong and Weak Acids
Strong Acids are strong electrolytes

HCl(aq) H+(aq) + Cl-(aq)

HNO3-(aq) H+(aq) + NO32-(aq)
HClO4(aq) H+(aq) + ClO4-(aq)
H2SO4(aq) H+(aq) + SO4-(aq)

Weak Acids are weak electrolytes

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

HNO2(aq) H+(aq) + NO2-(aq)
HSO4-(aq) H+(aq) + SO42-(aq)
H2O(l) H+(aq) + OH-(aq) 32
 Strong Acid (HCl) Weak Acid (HF)
HCl(aq) H+(aq) + Cl-(aq) HF(aq) H+(aq) + F-(aq)
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq) HF(aq) + H2O(l) H3O+(aq) + F-(aq)

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HCl(aq) H+(aq) + Cl-(aq) AcOH(aq) H+(aq) + AcO-(aq)

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 Strong and Weak Bases
• Bases can be either strong electrolytes or weak electrolytes.
• Strong bases completely break up into their ions:
NaOH (aq) à Na+(aq) + OH-(aq)

• Weak bases only partially break up into their ions:

NH3 (aq) + H2O(l) ó NH4+ (aq) + OH-(aq)
Weak bases don’t completely dissociate, they go to equilibrium!

§ The extent of dissociation has a dramatic effect on the reactivity of

bases.

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 Strong and Weak Bases
§ 6 Strong bases:
§ MOH, where M = Na, K, Li.
§ M(OH)2, where M = Ca, Sr, Ba.

§ Weak bases:
§ Any H+ acceptor that is not those six.
§ Other metal hydroxides, Mg(OH)2, Zn(OH)2, Co(OH)2, La(OH)3.
§ Ammonia (NH3).
§ Amines, such as CH3NH2, (CH3)2NH, C5H5N.

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 Strong and Weak Bases
Strong Bases are strong electrolytes

NaOH(s) Na+(aq) + OH-(aq)

KOH(s) K+(aq) + OH-(aq)

Ba(OH)2(s) Ba2+(aq) + 2OH-(aq)

Weak Bases are weak electrolytes

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

C5H5N(aq) + H2O(l) C5H5NH+(aq) + OH-(aq)
CO32-(aq) + H2O(l) CO3H-(aq) + OH-(aq)
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 Strong and Weak Acids/Bases
Strong Acids Strong Bases
1. HClO4
Hydroxides of group 1 and 2
2. H2SO4 metals: M(OH)1 or 2
3. HI (excluding Be, Mg, Rb, Cs)
4. HBr
5. HCl
6. HNO3
Everything else that is a
proton donor or acceptor is
a weak acid/base. 38
Example pH = -log [H+]

Calculate the pH of a pOH = -log [OH]

(a) 1.0 x 10-3 M HCl solution pH + pOH = 14
?
Strong or HCl(aq) H+(aq) + Cl-(aq)
weak acid?
1.0 x 10-3 M 1.0 x 10-3 M
pH = -log (1.0 x 10-3)
pH = 3.00

(b) 0.020 M Ba(OH)2 solution

?
Strong or Ba(OH)2(aq) 2OH-(aq) + Ba2+(aq)
weak base?
0.02 M 0.04 M

[OH-] = 0.040 M
pH = 14.00 – pOH = 12.60
pOH = -log 0.040 = 1.40 39
 Relative Strength of Acid-Base Pairs

AH + B- A- + BH
acid base conjugate conjugate
base acid
Acids/Bases Conjugate Bases/acids
Very Strong Very Weak
Strong Weak
Weak Strong
Very Weak Very Strong
_______________________________________
• Strong acids lose protons readily è weak conjugate bases;

• Weak acids do not lose protons readily è strong conjugate bases.

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Knowing relative strength allows us to:
Directly calc the pH of solution (if it is a strong acid/base).
Predict if the equilibrium will favor reactants or products. 41
 Acids: How Strong? How Weak?
Relative scale is not particularly useful.
Qualitative, not quantitative.
There has to be a better way!

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

Since the system is at equilibrium, we

can write an equilibrium expression.

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

Ka is the acid ionization constant

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 Acids: How Strong? How Weak?
[H+][A-]
Ka =
[HA]

Ka is the acid ionization constant

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

Stronger, Large Ka

Weaker acid, Smaller Ka

The value of Ka is very large for

strong acids and moderate or
acid
Ka small for weak acids.
strength 43
44
Example
Calculate the pH of a 0.036 M HNO2 (Ka = 4.5 x 10-4) solution:

Strong or HNO2(aq) H+(aq) + NO2-(aq)

weak acid?

[HNO2] = 0.036 M

HNO2(aq) H+(aq) + NO-2(aq)

Initial (M): 0.036 0.00 0.00
Change (M): -x +x +x
Equilibrium (M): 0.036 - x x x
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Example
HNO2(aq) H+(aq) + NO-2(aq)
Initial (M): 0.036 0.00 0.00
Change (M): -x +x +x
Equilibrium (M): 0.036 - x x x

x 2 + 4.5 × 10-4 x - 1.62 × 10 -5 = 0

2
-4.5 × 10-4 ± 4.5 × 10-4 - 4(1)(-1.62 × 10-5 )
x=
2(1)
= 3.8 × 10-3 M or -4.3 × 10 -3 M

[H+] = 3.8 x 10-3 M

pH = -log (3.8 x 10-3 )
= 2.42 46
Bases: How Strong? How Weak?
B-(aq) + H2O(l) BH(aq) + OH-(aq)

Since the system is at equilibrium, we can write

an equilibrium expression.

[BH][OH-]
Kb =
[B-]

Kb is the base ionization constant

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Bases: How Strong? How Weak?
[BH][OH-]
Kb =
[B-]

Kb is the base ionization constant

B-(aq) + H2O(l) BH(aq) + OH-(aq)

Strong base, Larger Kb

Weaker base, Smaller Kb

base
Kb
strength
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 Bases: How Strong? How Weak?
Base Formula Kb Conj. Acid
Ethylamine C2H5NH2 5.6´10-4 C2H5NH3+
Methylamine CH3NH2 4.4´10-4 CH3NH3+
Base strength

Ammonia NH3 1.8´10-5 NH4+

Pyridine 1.7´10-9 C5H5NH+

Aniline C6H5NH2 3.8´10-10 C6H5NH3+

H
Caffeine 5.3´10-14 +

Solve weak base problems like weak acids

except solve for [OH-] instead of [H+]. 49
Example
What is the pH of a 0.40 M NH3 solution (Kb = 1.8´10-5)?

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

Kb = 1.8´10-5

[NH3]0 = 0.40 M

pH = ?

1) We have the information to find OH.

2) We can use OH to find pH.

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 Ka and Kb
HA(aq) H+(aq) + A-(aq) A-(aq) + H2O(l) AH(aq) + OH-(aq)

[H+][A-] [AH][OH-]
Ka = Kb =
[HA] [A-]

For a acid-base conjugate pair in water:

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
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 Kw, Ka and Kb Summary

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

Ka = Kb =
[HA] [A-] Kw = 1 x 10-14

Weak Acid and Its Conjugate Base

Kw Kw
KaKb = Kw Ka = Kb =
Kb Ka

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53
The Ka for formic acid (HCOOH) is 1.7x10-4. What
is Kb for HCOO-?

KaKb = Kw

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

acid ionization constant percent ionization =

[H+][A-] [H+] at equilibrium
Ka = x 100%
[HA] Initial concentration of [HA]
acid
Ka [H+]
strength Percent ionization = x 100%
[HA]0

Percent ionization:
• Strong acids- % ionization is always 100%

• Weak acids- % ionization decreases as

concentration increases.
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 Percent Ionization
A certain weak acid, HA , has a Ka value of 9.2 x 10¯7
1) Calculate the percent ionization of HA in a 0.10 M solution.
2) Calculate the percent ionization of HA in a 0.010 M solution.
3) Calculate the percent ionization of HA in a 0.0010 M solution.
Question 1:

Question 2:

Question 3:
[HA] % ion
56
% ionization change with concentration . Ka stays the same!
 Acid/Base Strength
Some factors that influence acid/base strength (Ka/Kb).
• Temperature
[H+][A-] kfwd
Ka = = k = Ae Ea /RT
[HA] krev

• Solvent

• Acid Structure
– Hydrohalic acids
– Oxoacids
– Carboxylic acids

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 Hydrohalic Acid Strength
§ The strength of an acid depends on the strength of the X–H
bond that is to be broken.
§ Relative bond strength: For H-X,
electronegativity does
H─F > H─Cl > H─Br > H─I not play a big role.
§ Relative acid strength:
H─F < H─Cl < H─Br < H─I

Ka
7.2 x 10-4
~107
~109
~109

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 Oxoacid Strength
Oxoacids is an acid that contains oxygen and a central atom Z.
d- d+
Z O H Z O- + H+

The O-H bond strength/Ka are dependent on:

• electronegativity of Z
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• oxidation state of Z
 Oxoacid Strength
Oxoacids is an acid that contains oxygen and a central atom Z.

If they are from the same group and have the same
oxidation number, acid strength increases with increasing
electronegativity of Z.
Cl is more electronegative than Br

acidity
HClO3 > HBrO3
increases

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 Oxoacid Strength
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

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 Carboxylic Acid Strength
General structure for a carboxylic acid:

Where R can be anything: H, CH3, Ph, Cl…

The more
electrongative R is
the stronger the
carboxylic acid.

Proximity of the
electrongative
atom matters.
62
Question:
What is the strongest acid:
BrOH ClOH IOH
A B C

A B

CH3OH CBr3OH CF3OH

A B C
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