ACID AND BASE

Objectives

Understand different concepts of acid and base Understand concept p of strong g acid/base / and weak acid/base

Acid Base concepts

1 Arrhenius 1. A h i definition d fi iti : An A acid id is i a substance b that h dissociates di i in i water to produce H+ ions (protons), and a base is a substance that dissociates in water to produce OH ions (hydroxide); an acid-base reaction involves th reaction the ti of f a proton t with th the hydroxide h d id ion i to t form f water w t 2. BrnstedLowry definition: An acid is any substance that can donate a proton proton, and a base is any substance that can accept a proton; proton acid-base reactions involve two conjugate acid-base pairs and the transfer of a proton from one substance (the acid) to another (the base) 3. Lewis definition: A Lewis acid is an electron-pair acceptor, and a Lewis base is an electron-pair donor

Arrhenius definition

An acid is a substance that, when dissolved in water, increases the concentration of hydronium ion (H3O+). A base is a substance that, , when dissolved in water, increases the concentration of hydroxide ion, (OH).

The Arrhenius Arrheni s concept is limited in that it looks at acids and bases in aqueous solutions only. only

Strong Acids and Bases

In the Arrhenius concept, a strong acid is a substance that ionizes completely in aqueous solution to give H3O+ and an anion. Example p of strong g acids include HCl, , HBr, , HI, , HNO3 , and H2SO4.

HClO4(aq) 4( ) + H 2 O (l) H 3O

+ (aq) ( )

+ ClO

4 (aq) ( )

Strong Acids and Bases

In the Arrhenius concept, a strong base is a substance that ionizes completely in aqueous solution to give OH and a cation. Example p of strong g bases include LiOH, , KOH, , Ca(OH)2, Sr(OH)2, and Ba(OH)2.

NaOH (aq) Na
H2O

+ (aq)

+ OH

(aq)

Weak Acids and Bases

Most other acids and bases that we encounter are weak.

They

are not completely ionized and exist in reversible reaction with the corresponding ions.

Examples are acetic acid and ammonium hydroxide

CH3COOH (aq) + H 2O(l) H3O+ (aq) + CH3COO (aq)

+ NH 4 OH (aq) NH 4 (aq) + OH (aq ) H2O

Brnsted-Lowry Brnsted Lowry Concept

An acid is the species donating the proton in a proton-transfer reaction. A base is the species accepting the proton in a proton-transfer reaction.

In any reversible acid-base reaction, both forward and reverse reactions involve proton transfer.

Brnsted-Lowry Brnsted Lowry Concept

Consider the reactions:

H H Cl H O H H O H Cl

Acid

Base

H H Cl H N H H H N H H Cl

Acid

Base

Brnsted-Lowry Brnsted Lowry Concept

Consider the reaction of NH3 and H2O.

H H N H H H O H H N H H O H

B Base

A id Acid

A id Acid

B Base

In the forward reaction, H2O donates a p proton to NH3. The H2O molecule is the acid and NH3 molecule is the base. In the reverse reaction, NH4+ donates a proton to OH-. The NH4+ ion is the acid and OH- is the base.

Conjugate acid acid-base base pair

A conjugate acid-base pair consists of two species in an acid-base reaction, one acid and one base, that differ by the loss or gain of a proton.

The conjugate base of an acid is a species that remains when one proton has been removed from the acid. Th conjugate The j t acid id of fab base i is a species i th that t results from the addition of one proton to a base.

O H3C C O H H O H H

H O H H3C

O C O

Acid

Base

Acid

Base

Conjugate acid-base acid base pair

Conjugate base of an acid: species that remains when one proton has been removed from the acid Conjugate acid of a base: species that results from the addition of one p proton to a base

O H3C C O H H O H H

H O H H3C

O C O

Acid

Base

Acid

Base

Conjugate base of CH3COOH = CH3COOConjugate acid of H2O = H3O+

See example 3.1

Amphiprotic species

An amphiprotic species is a species that can act either as an acid or a base ( it can gain or lose a proton ).
Example

is water.
H+

O H

O H

Acid

Base

Lewis Concept

An acid is an electron pair acceptor A base is an electron p pair donor.

F H N H H F F B F H N H H B F

acid

base

o Boron trifluoride accepts the electron pair, so it is a Lewis acid. Ammonia donates the electron pair, p so it is the Lewis base.

Relative Strength of Acids and Bases

Strong acid

HCl(aq) + H 2 O(l) H3O+ (aq) + Cl (aq)

CH3COOH (aq) + H 2O(l) H3O+ (aq) + CH3COO (aq)

Weak acid o The Th stronger t acids id are those th that th t lose l their th i hydrogen ions more easily than other acids. o Similarly, the stronger bases are those that hold onto hydrogen ions more strongly than other bases. bases

Relative Strength of Acids and Bases

Comparing conjugate acid-base pairs:

The stronger the acid, the weaker its conjugate base. The stronger the base, the weaker its conjugate acid. An acid-base reaction is favoured in the direction from the stronger member to the weaker member of each conjugate acid-base pair.
See table 3.1

Self-ionization Self ionization of Water

Self-ionization is a reaction in which two like molecules react to give ions.

In the case of water, the following equilibrium is established.

H 2O(l) + H 2O(l) H3O+ (aq) + OH (aq)

The equilibrium-constant expression for this system is:

K w = [H 3O + ][OH ]
At 25 oC, the value of Kw is 1.0 x 10-14

Self-ionization Self ionization of Water

With Kw value, we can calculate [H+] and [OH] in pure water

These

ions are produced in equal numbers in pure water, so if we let x = [H+] = [OH]

1.0 10

14

= (x)(x)

at 25 C

[H 3O + ] = [ [ [OH ] = 1.0 10 7 M
o If we add acid or base to water, water [H+] [OH] but the Kw expression still holds.

[H3O+] and [OH] in aqueous solution

In aqueous solution, [H3O+] and [OH] is related by the Kw value. value In the solution above, the [H3O+] is approximated to 0.00015 M K We can calculate [OH] from [OH ] = w +
[H 3O ] 1.0 1014 = = 6.7 1011 M 0.00015

pH and pOH

The pH of a solution is defined as the negative of the common logarithm of [H3O+].

pH = log[H 3O ]
We can also get pOH as

pOH = log[OH ]
pKw K = l log([H ([H3O ][OH ]) = log(1.0 l (1 0 10 pKw = ( log[H p g[ 3O + ]) + ( log[OH g[ ]) = 14 pKw = pH + pOH = 14
+ 14

The pH of a Solution

In a neutral solution, [H3O+] is 1.0 x 10-7, the pH = 7.00. For acidic solutions, solutions [H3O+] >1.0 >1 0 x 10-7, so the pH is less than 7.00. Similarly, a basic solution has a pH greater than 7.00.

The pH of a Solution

For a solution in which the hydrogen-ion concentration is 1.0 x 10-3, the pH is:

pH = log(1.0 10 ) = 3.00

N Note t that th t the th number b of f decimal d i l places l i th in the pH H equals the number of significant figures in the hydrogen-ion concentration.

Example 3.5

The pH of human arterial blood is 7.40. What is the hydrogen hydrogen-ion ion concentration?

[H ] = 10 [H ] = 10
+ ( 7.40)

( pH) 8

= 4.0 10 M

Question:

An ammonia solution has a hydroxide-ion concentration of 1.9 x 10-3 M. What is the pH of the solution?

W fi We first calculate l l the h pOH: OH

pOH OH = log(1.9 l (1 9 10 ) = 2.72 2 72

Th the Then th pH Hi is:

pH = 14.00 2.72 = 11.28 p

Acid ionization constant (Ka)

HA (aq) + H 2 O(l) H3O+ (aq) + A (aq)
HA (aq) H + (aq) + A (aq)

the acid ionization constant (Ka) is

H 3O A Ka = [ HA ]
+

or

+ H A Ka = A] [ HA

Base ionization constant (Kb)

B(aq) + H 2 O(l) BH
+ (aq)

+ OH

(aq)

the base ionization constant (Kb) is

+ BH OH Kb = [ B]

Ka and Kb values

We can use Ka and Kb values to compare the W strengths of acids and bases.
The

larger Ka, the stronger is the acid and the greater the [H+] at equilibrium. The Th larger l Kb, the th stronger t is i the th base b and d th the greater the [OH-] at equilibrium.

pK a = log p g Ka pK b = log K b

Low values of pKa and pKb

correspond to large values of Ka and Kb. Thus, the stronger acid, the lower is the pKa

See table 3.2

The relationship between conjugate acid-base i i i constants ionization

Consider

For a conjugate acid-base acid base pairs

Ka Kb = Kw

Percent ionization

The degree of ionization is the fraction of the acid molecules that ionize. Percent ionization gives the proportion of ionized molecules on a p percentage g basis.
[H3O + ] derived from HA Degree of ionization = initial [HA]

[H3O + ] derived from HA 100 Percent ionization = initial [HA]

Acid Base Calculation

Calculation for strong acid and base C l l i f Calculation for weak k acid id and db base (involve (i l acid base equilibrium)

Solutions of Strong Acid or Base

In a solution of a strong acid we can normally ignore the self-ionization of water as a source of H+.
The [H+]is Th ]i usually ll determined d t i db by th the strong t acid id concentration. o However, the self-ionization still exists and is responsible for a small concentration of OH- ion.

Solutions of Strong Acid or Base

Example, calculate the concentration of OH- ion in 0.10 M HCl.

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

Because we started with 0.10 M HCl ( a strong acid ) the reaction will produce 0.10 M H+(aq). Substituting [H+]=0.10 into the ion-product expression, we get:

1 0 1014 = (0 1.0 (0.10)[OH 10)[OH ]

-14 1.0 1 0 10 13 [OH ] = = 1.0 10-13 M 0.10

Solutions of Strong Acid or Base

Similarly, in a solution of a strong base we can normally ignore the self-ionization of water as a source of OH.
The [OH] is Th i usually ll d determined t i db by th the strong t b base concentration.

o However, the self-ionization still exists and is responsible for a small concentration of H+ ion.

Solutions of Strong Acid or Base

Example, calculate the concentration of H+ ion in 0.010 M NaOH. H2O NaOH(s) Na + (aq) + OH (aq)

Because we started d with h 0.010 0 0 0 M NaOH N O ( a strong b base ) the h reaction will produce 0.010 M OH-(aq). S b Substituting [O ]=0.010 [OH ] 0 0 0 into the h ion-product d expression, we get:

1 0 10 14 = [H + ](0.010) 1.0 ](0 010)

-14 1.0 10 12 [ +] = [H = 1.0 1 0 10-12 M 0.010

Solutions of Weak Acid or Base

For weak acid and base, the calculation will involve acid-base equilibrium. The acid-base equilibrium calculations are much like those of the chemical equilibrium q chapter. p
The

ICE table is always useful in calculation equilibrium p ob e s. problems.

See examples 3.7 3.10

Polyprotic acid

Acid that can release more than one proton (H+) Example:

We can see that Ka1 >> Ka2 See example 3.11

Acid-Base Acid Base Properties of Salt Solutions

Salts are strong electrolytes that completely dissociate in water The pH of the solution depends on the hydrolysis of ions. The term salt hydrolysis describes the reaction of an anion or a cation of a salt, salt or both, both with water water. Salt hydrolysis usually affects the pH of a solution.
Concentration

of hydrogen ion or hydroxide ion has been changed.

Salts of strong acid and base

When dissolve in water will produce neutral solutions No hydrolysis

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

N Na Cl

+ (aq) (aq)

+ H 2 O(l) no reaction ti

pH =7

+ H 2 O(l) no reaction

Salts of a strong base weak acid

When dissolve in water will produce basic solutions Hydrolysis of conjugate base of the weak acid.

H2O NaCN (s) Na + (aq) + CN (aq)

CN (aq) + H 2O(l) HCN (aq) + OH (aq)

Hydroxide ion increases See example 3.12

pH > 7

Salts of a weak base strong acid

When dissolve in water will produce acedic solutions Hydrolysis of conjugate acid of the weak base.
H2O

NH 4 Cl l(s) NH 4 + (aq) + Cl l (aq)

NH 4 + (aq) + H 2O(l) NH3(aq) + H3O+ (aq)
Hydronium ion increases

pH < 7

Buffer

A buffer solution is a solution of a weak acid or a weak base and its salt. The solution has the ability to resist changes in pH upon p p the addition of small amounts of either acid or base. A buffer system can be represented as salt/acid or conjugate base/acid.
The Th

sodium di acetate-acetic t t ti acid id b buffer ff system t can b be written as CH3COONa/CH3COOH or CH3COO/CH3COOH.

How does buffer work?

Buffer solution consists of weak acid (HA) and its conjugate base (A)
When

acid is added, it is consumed by reacting with A-

HA

A-

A- + H3O+ HA + OH-

How does buffer work?

Buffer solution consists of weak acid (HA) and its conjugate base (A)
When

base is added, it is consumed by reaction with HA

HA

A-

HA + OH-A- + H2O

How a buffer works

How does buffer work?

Adding small amount of acid or base does not change [H3O+] of the solution. Since pH = -log [H3O+] , then the pH of the solution is almost unchanged. g However, there is a limit in which the buffer can withstand the change of pH. pH
This

is called buffer capacity. Buffer B ff capacity i d depends d on the h amount of f acid id and d conjugate base in the solution.

Calculation Ca cu a o pH p o of bu buffer e solution so u o

Consider buffer ff solution of f acetate ion/acetic / acid

CH 3COOH + H 2 O H 3O + + CH 3COO
+ H O CH COO 3 3 Ka = [CH3COOH ]

HendersonHasselbalch Equation

CH COO 3 pH = pKa + log [CH3COOH ]

conjugate j g base ] [ pH H = pKa K +l log [ weak acid ]

pH range for buffer

In general, the pH range over which a buffer solution is most effective is about one pH unit on either side of pH = pKa. This corresponds p to the ratios
conjugate base] [ 0 10 < 0.10 < 10.0 10 0 [ weak acid ] conjugate base ] [ 1.0 < log < 1.0 [ weak acid ]

pH of buffer
Example 3.13

Instructions for making up a buffer say to mix 60 mL of 0.100 M NH3 with 40 mL of 0.100 M NH4Cl. What is the pH of this buffer?