CHAPTER 7

Acid And Base Equlibria

Professor Dr. Ibrahim Badr

 OUTLINE

7.(1-4 ) Acid-Base Theories

7.5 pH of BLOOD

7.6 Weak acids and bases. What is the pH?

7.7 Salts of weak acids and bases. Are not neutral.

7.8 Buffers-Keeping the pH constant

7.13 Physiological buffers-They keep you alive.

 7-(Units 1-4)
Acid-Base Theories

Bronsted Lowery Definition of Acids and Bases:

Acids are proton donors:

HCl + H2O → H3O+ + Cl-

H2SO4 + H2O →HSO4- + H3O+

Bases are proton acceptors (or hydroxyl group donors)

NH3 + H2O → NH4+ + OH-

Salts are formed by acid-base reactions
(Salts are strong electrolytes)
Acid + Base → Salt

NH3 + HCl → NH4Cl

CH3COOH + NH3 → CH3COO- + NH4+

Weak Acid Conjugate Base
Weak Base Conjugate Acid
 WHAT ARE ACIDS AND BASES

Lewis Definition of Acids and Bases:

Acids are electron acceptors :

H+ + :NH3 → NH4+

Bases are electron donors

:NH3 + H+ → NH4+

Arrhenius Definition of Acids and Bases (applies only to aqueous

solutions)

Acids are H+ donors

Bases are OH- donors

 RELATIONSHIP BETWEEN [H+]&[OH-], and pH

Water acts as both weak acid and weak base “autopyrolysis”

H2O + H2O → H3O+ + OH-

Hydronium ion Hydroxyl ion

This equilibrium can be described by the equilibrium constant of water Kw

Kw = [H+] . [OH-]=10-14 mol/L @ 25 oC

pKw = pH + pOH = 14

pH = pOH =7 @ 25 oC
 The pH definition

By definition:

p(Value)=-log(Vaule)

pH=-log[H+] pOH=-log[OH-]

pH Scale:
@ 25 oC

7.0
 7.5 pH scale at 37 oC (Blood pH)

Blood temperature is 37 oC

Kw = [H+] . [OH-]=2.5 x 10-14 mol/L @ 37 oC

pKw = pH + pOH = 13.6

pH=pOH=6.80

6.8
For this reason, measurement of blood pH for
diagnostic purposes is generally done at 37◦ C
 7.6 Weak acids and bases. What is the pH?

Strong Acids/Bases
Dissociate completely in water. For example
HCl, H2SO4, HBr, HClO4, NaOH, KOH
HCl ➔ H+ + Cl-
Weak Acids/Bases

Dissociate Partially in water. For example

CH3COOH, NH4OH

CH3COOH  H+ + CH3COO-

The strength of acids and bases is given by Ka and Kb respectively.

This equilibrium: HA  H+ + A- Can be described by Ka:

+ −
[H ]  [ A ]
Ka =
[ HA ]
 STRENGTH OF ACIDS AND BASES

+ −
[H ]  [ A ]
Ka =
[ HA ]
As the value of Ka increases the acid strength increases (i.e., the amount
of hydrogen ion generated by the acid). Also the acid strength can be
expressed in terms of pKa, where:
pKa=-logKa

pKa Acid strength

Ka

Similarly for a weak base, the base strength is given by Kb and pKb.

pKb Base strength

Kb

Ka . Kb=10-14
 pH of strong acids and bases

EXAMPLE 7.3

EXAMPLE 7.5
 pH of Weak Acids & Bases

Weak acids dissociate partially in water giving less amount of

H +.

HA  H+ + A-
At time=0 CHA 0.0 0.0
At equilibrium CHA-x x x

2
[ x]
Ka =
[C HA − x]
If CHA > 100 Ka If not Solve quadratic
(X ) can be neglected equation
compared to CHA for (x)= H+

+ − b + b2 − 4ac
H = Ka.CHA x=
2a
 EXAMPLE:
Find the pH of 0.0200 M benzoic acid (Ka= 6.28 x 10-5)

SOLUTION
HA  H+ + A-
At time=0 0.0200 0.0 0.0
At equilibrium 0.0200-x x x
2
[ x]
6.28 •10 = −5

[0.0200 − x]
1 [ x ]2 + 6.28 •10−5 • x − 1.256 •10−6 = 0
a=1 b=Ka c=-Ka*Conc

Solve quadratic equation and the positive solution is the [H+].

x = 1.09 * 10-3 M pH = -log(1.09 * 10-3) = 2.96

 pH of Weak Base

Weak acids dissociate partially in water giving less amount of

OH-.

B + H2O  BH+ + OH-

At time=0 CB 0.0 0.0
At equilibrium CB-x x x x = [OH-]

If CB> 100 Kb If not Solve quadratic

(X ) can be neglected equation
compared to CHA for (x)= OH-

− − b + b2 − 4ac
x = [OH ] = K b.C B x=
2a
EXAMPLE:
Find the pH of 0.0372 M cocaine (Kb= 2.6 x 10-6)

SOLUTION
B +H2O  BH+ + OH-
At time=0 0.0372 0.0 0.0
At equlibrium 0.0372-x x x

2
[ x ]
2.6 •10−6 =
[0.0372 − x]
2
[ x ]
Cb  100 K b Then : 2.6 •10−6 =
0.0372

x = [OH- ] = 3.1 * 10-4 M pOH = -log(3.1 * 10-4)= 10.45

 7.6 pH of Salts of Weak acids and Bases

Salts of strong acids and strong bases are neutral: NaCl, K2SO4

Salts of weak acids and strong bases are basic: CH3COONa

Treat as bases when calculating the pH

−
[OH ] = K b.CA - If CA- > 100 Kb
Otherwise solve Quad. Eqn

Salts of strong acids and weak bases are basic: NH4Cl

Treat as acids when calculating the pH

+
[H ] = K a.CBH + If CBH+ > 100 Ka
Otherwise solve Quad Eqn
 Examples

EXAMPLE 7.9:
Find the pH of 0.1 M sodium acetate (Kb=5.7 x 10-10)

SOLUTION
CH3COO- + H2O  CH3COOH + OH-
At time=0 0.1 0.0 0.0
At equlibrium 0.1- x x x

2
[ x ]
5.7 • 10−10 =
[0.1 − x ]
2
[x]
Cb  100 Kb Then : 5.7 • 10−10 =
0.1

x = [OH- ] = 7.6 x 0-6 M pOH = -log(7.6 x 10-6)= 5.12

pH=14 - 5.12=8.88
 Examples

EXAMPLE 7.9:
Calculate the pH of 0.25 ammonium chloride. Ka=5.7 x 10-10

SOLUTION
NH4+ + H2O  NH3 + H3O-
At time=0 0.25 0.0 0.0
At equlibrium 0.25- x x x

2
[ x ]
5.7 • 10−10 =
[0.25 − x ]
[x]2
Cb  100 Kb Then : 5.7 • 10 = −10

0.25

x = [H+ ] = 1.2 x 0-5 M pH = -log(1.2x 10-5)= 4.92

 7.7 Buffers

• Buffer is a solution of weak acid/base and

its conjugate base/acid.
• Buffer resists change in the pH of
solution which is very important in many
chemical and biological processes.
• Give example for the importance of pH
control.
• Give examples of buffer systems.

Classroom discussion.
• How buffer works?

OH- H+

HA + H2O A- + H3O+
Acid
Conjugate Base

◼ The added acid reacts with the conjugate base.

◼ The added base reacts with the weak acid.
◼ The concentration of hydrogen ion remain INTACT (Unchanged).
 Henderson Equation

❖ Weak acid + Conj. Base. ❖ Weak base + Conj. acid.

HA + H2O <--> A- + H3O+ B + H2O <--> BH+ + OH-

−
+ −
[H ]  [ A ] [OH ]  [ BH + ]
Ka = Kb =
[ HA ] [B ]
−
[A ] [B]
pH = pK a + log pH = pK a + log
[ HA ] [ BH + ]
Henderson eqn. Henderson eqn.
[proton acceptor ]
pH = pKa + log
[proton donor]
 Examples

EXAMPLE 7.11

SOLUTION

p
 Examples

EXAMPLE 7.12

SOLUTION
 Preparation of Buffer Solution

STRONG
BASE

HA -
HA++AA-
HA
HA Weak
Weakacid
acid++Conjugate
ConjugateBase
Base
WEAK
WEAKACID
ACID BUFFER!!!
BUFFER!!!

OR
STRONG
ACID

BH +
BB BH+++BB
Weak
Weakbase
base++Conjugate
Conjugateacid
acid
WEAK
WEAKBASE
BASE BUFFER!!!
BUFFER!!!

Give an example for each case.

 Preparation of Buffer Solution

Example
What volume of 3.0 M sodium hydroxide should added to
ammonium chloride to prepare 500 mL of buffer pH 9.5 with salt
concentration 0.1 M

Solution
NH4+ + OH- NH3+ H2O
Conjugate Acid Base

[ NH 3 ] [ NH 3 ] [ NH 3 ]
pH = pKa + log +
 9. 5 = 9 . 24 + log +
 log +
= 0.26
[ NH 4 ] [ NH 4 ] [ NH 4 ]
[ NH 3 ]
+
= 1.8  [ NH 3 ] = 1.8  0.1 = 0.18M = concentration of NaOH
[ NH 4 ]

Volume NaOH = 0.18 x 500/3 = 30 mL

 Buffer capacity

Buffer capacity is a measure of how well a buffer resists the change in

pH when acid or base is added. The larger is the buffer capacity the
smaller is the pH change.

Capacity

Capacity depends on:

1- Concentration
2- Ratio (salt/acid)

-1 0 1
log(salt/acid)
The buffer range is pH=pKa±1
Outside this range the solution is NOT buffered
 7.9 Physiological Buffers-keeps us alive

• Homeostasis of pH is tightly controlled

• Extracellular fluid = 7.4
• Blood = 7.35 – 7.45
• <6.8 or > 8.0 death occurs
• Acidosis (acidemia) below 7.35
• Alkalosis (alkalemia) above 7.45
7.9 Physiological Buffers-keeps us alive

27
7.9 Physiological Buffers-keeps us alive

28
 HOMEWORK ASSINGMENT

6, 7, 10, 11,19, 23,

28, 32, 34, 45, 48, 53