ACIDS,BASES & BUFFERS

Theories of acids & bases

There are three distinct theories that describe
acid-base phenomenon namely
• Arrhenius theory
• Lewis
• Lowry Bronsted theory
 Arrhenius theory
• This theory define acids and bases according to
there formation of ions when dissolved in
water.
• An acid is a substance that can release
hydrogen ion (H+) when dissolved in water e.g.
HCL(H+ + CL-)
• A base is a substance that can release a
hydroxyl ion (OH-) when dissolved in water e.g
NaOH( Na+ + OH-)
 Limitation of Arrhenius theory
• Water is essential
• Doesn’t explain acidity or basicity of non
aqueous solvents e.g. benzene
• Basicity of ammonia (No OH-) is not explained
• Acidity of BF3,Alcl3 (No H+ ion ) is not explained
 Lewis theory
• Acids is a molecule or ion that accept the lone
pair of electrons
• Example : H+ ,NH4+,C++,Al+++

• Base is the molecule or ion that donate the

lone pair of electrons
• Example: OH-,Cl-,CN-
 Lowry Bronsted theory
• An a cid is the substance which donate proton
• A base is a substance which donate proton
• HA + H2O(l) A-(aq) + H3O+(aq)
• Acid base conjugate base hydronium
• B(aq) + H2O(l) BH+ + OH-(aq)
• Base Acid conjugate acid hydroxide
ion
 Conjugate Acid-Base Pairs
• According to Bronsted-Lowry theory ,a
conjugate acid-base consists of molecules or
ions related by loss of one H+ by an acid and
gain of one H+ by a base.
• Every acid-base reaction contains two
conjugate acid-base pairs because H+ is
transferred in both the forward and reverse
reaction direction
 Conjugate Acid-base
• When an acid such as HF loses one H+,the
conjugate base is F- is formed. When a base
such as H2O gains and an H+,its conjugate
acid ,H3O+, is formed
• Because the overall reaction of HF is
reversible, the conjugate acid H3O+ can donate
H+ to conjugate base F- and reform the acid HF
and the base water,H2O
 Conjugate-Acid base
• HF, an acid, loses one H+ to form its conjugate base
F-.
• Water acts as a base by gaining one H+ to form its
conjugate acid H3O+.
• HF + H2O F- + H3O+

Acid Base Conjugate conjugate

base acid
 Conjugate acid base
• Ammonia, NH3, acts as a base when it gains
one H+ to form its conjugate acid NH4+.
• Water acts as an acid by losing one H+ to form
its conjugate base OH-.

• NH3(g) + H2O NH4+ + OH-

Base acid conjugate conjugate
acid base
 Assignment
• Identify the conjugate acid-base pairs in the
following reaction
• HBr(aq) + NH3(aq) Br- + NH4(aq)

• HCN + SO42- CN- HSO4-

• H3PO4 + H2O H2PO4- + H3O+
• CO32- + H2O HCO3- + OH-
Strong and Weak Acids
Strong acids are examples of strong electrolytes because
they donate H+ so easily that their dissociation in water is
essentially complete. For example, when HCl, a strong acid,
dissociates in water, H+ is transferred to H2O; the resulting
solution contains essentially only the ions H3O+ and Cl-. We
consider the reaction of HCl in H2O as going 100% to
products. Thus, one mole of a strong acid dissociates in
water to yield one mole of H3O+ and one mole of its
conjugate base. We write the equation for a strong acid such
as HCl with a single arrow.
HCl(g) + H2O(l) H3O+(aq) + Cl-(aq)
There are only six common strong acids, which are stronger
Acid Conjugate Base
Strong acids(relative strength decrease downwards)
Hydroiodic aicd HI I- Iodide
Hydrobromic acid HBr Br- Bromide
Hydrochloric acid Hcl Cl- Chloride
Sulfuric acid H2SO4 HSO4- Hydrogen sulphate
Nitric acid HNO3 NO3- Nitrate
Perchloric acid HCLO4 CLO4- Perchlorate
Hydronium ion H3O+ H2 O Water
Weak acids
Hydrogen sulfate ion HSO4- SO42- Sulfate ion
Phosphoric acids H3PO4 H2PO4- Dihydrogen phosphate
Nitrous acids HNO2 NO2- Nitrite ion
Hydrofluoric acids HF F- Fluoride
Weak Acids Formula Conjugate Conjugate base(ion)
base
Acetic acid CH3COOH CH3COO- acetate
Carbonic acid H2CO3 HCO3- Bicarbonate
Hydrosulfuric acid H2 S HS- Hydrogen sulfide
Dihydrogen phosphat H2PO4- Hydrogen phosphate
HPO42-
Ammonium ion NH4+ NH3 ammonia
Hydrocyanic acid HCN CN- Cyanide ion
Bicarbonate ion HCO3- CO32- Carbonate ion
Methylammonium ion CH3-NH3+ CH3-NH2 methylamine
Hydrogen phosphate HPO42- PO43- phosphate
ion
Water H2 O OH- Hydroxide ion
NB: Relative acid strengths decreases downwards & base strengths
Diprotic Acids
Some weak acids, such as carbonic acid, are diprotic acids that
have two H+, which dissociate one at a time. For example,
carbonated soft drinks are prepared by dissolving CO2 in water
to form carbonic acid (H2CO3). A weak acid such as H2CO3
reaches equilibrium between the mostly undissociated H2CO3
molecules and the ions H3O+ and HCO3-.
H2CO3(aq) + H2O(l ) H3O+(aq) + HCO3- (aq)
Carbonic acid Bicarbonate ion(hydrogen carbonate)
Because HCO3- is also a weak acid, a second dissociation can
take place to produce another hydronium ion and the carbonate
ion (CO32-).
HCO3-(aq) H2O(l) H3O+(aq) + CO3 2-(aq)
Bicarbonate ion carbonate ion
Sulfuric acid (H2SO4) is also a diprotic acid. However, its first
dissociation is complete (100%), which means H2SO4 is a
strong acid. The product, hydrogen sulfate (HSO4-) can
dissociate again but only slightly, which means that the
hydrogen sulfate ion is a weak
acid.
H2SO4(aq) + H2O(l ) HSO4-(aq) + H3O+(aq)
Sulfuric acid Bisulfate ion (hydrogen sulfate)

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

Bisulfate ion Sulfate ion
(hydrogen sulfate)
In summary, a strong acid such
 Summary
•In summary, a strong acid such as HI in water dissociates
completely to form an aqueous solution of the ions H3O+ and
I-. A weak acid such as HF dissociates only slightly in water to
form an aqueous solution that consists mostly of HF molecules
and a few H3O+and F- ions .
•Strong acid: HI(aq) + H2O(l) H3O+(aq) + I-(aq) Completely
dissociated
•Weak acid: HF(aq) + H2O(l) H3O+(aq) + F - (aq) Slightly
dissociated
•NB: complete reaction represented by one arrow running from
left to right. Reversible reaction represented by two arrow
pointing opposite direction
Strong and Weak Bases
As strong electrolytes, strong bases dissociate completely
in water. Because these strong bases are ionic
compounds, they dissociate in water to give an aqueous
solution of metal ions and hydroxide ions. The Group 1A
(1) hydroxides are very soluble in water, which
can give high concentrations of OH- ions. A few strong
bases are less soluble in water, but what does dissolve
dissociates completely as ions. For example, when KOH
forms a KOH solution, it contains only the ions K+ and
OH-.H2O
KOH(s) K+(aq) + OH-(aq)
Strong Bases
Lithium hydroxide (LiOH)
Sodium hydroxide (NaOH)
Potassium hydroxide (KOH)
Rubidium hydroxide (RbOH)
Cesium hydroxide (CsOH)
Calcium hydroxide (Ca(OH)2)*
Strontium hydroxide (Sr(OH)2)*
Barium hydroxide (Ba(OH)2)*
*Low solubility(Group 2) alkaline earth
metals
The remaining of the bases are weal
Direction of Reaction
There is a relationship between the components
each conjugate acid–base pair. Strong acids have
weak conjugate bases that do not readily accept H
As the strength of the acid decreases, the strengt
its conjugate base increases.
In any acid–base reaction, there are two acids and
two bases. However, one acid is stronger than the
other acid, and one base is stronger than the othe
base. By comparing their relative strengths, we ca
determine the direction of the reaction.
For example, the strong acid H2SO4 readily gives up
H+ to water. The hydronium ion H3O+ produced is a
weaker acid than H2SO4, and the conjugate base
HSO4 - is a weaker base than water.
H2SO4(aq) + H2O(l ) H3O+(aq) + HSO4- (aq) Mostly products
Stronger Stronger Weaker Weaker
acid base acid base
Let’s look at another reaction in which water donates one H+
to carbonate (CO32-) to form HCO3 - and OH-. From previous
tables, we see that HCO3 - is a stronger acid than H2O.We
also see that OH- is a stronger base than CO32-. To reach
equilibrium, the stronger acid and stronger base react in the
direction of the weaker acid and weaker base.
CO32-(aq) + H2O(l ) HCO3- (aq) + OH-(aq) Mostly reactants
Weaker Weaker Stronger Stronger
base acid acid base
 Assignment/Exercise
1.Does the equilibrium mixture of the following reaction contain mostly
reactants or products?
HF(aq) + H2O(l ) H3O+(aq) + F-(aq)
2.What is meant by the phrase “A strong acid has a weak conjugate base”?
3. What is meant by the phrase “A weak acid has a strong conjugate base”?
4.Identify the stronger acid in each of the following pairs:
• a. HBr or HNO2 b. H3PO4 or HSO4-
• c. HCN or H2CO3
5.Write an equation for the acid base reaction between ammonium ion and
sulfate ion. Why does equilibrium mixture mostly contain products
 Dissociation constants
Consider reaction A + B C + D
According to law of mass action
K=([C]*[D])/([A]*[B])
i.e. products/reactant
[ ]=Concentration
Dissociation constant for acids(Ka)
Acids have different strengths depending on how much
they dissociate in water. Because the dissociation of
strong acids in water is essentially complete, the reaction
is not considered to be an equilibrium situation.
However, because weak acids in water dissociate only
slightly, the ion products reach equilibrium with the
undissociated weak acid molecules. For example, formic
acid (HCHO2) the acid found in bee and ant stings, is a
weak acid. Formic acid is a weak acid that dissociates in
water to form hydronium ion (H3O+) and formate ion
(CHO2-).
HCOOH + H2O HCOO- + H3O+
Writing Dissociation Constants
An acid dissociation expression, Ka, can be written for weak acids
that gives the ratio of the concentrations of products to the weak
acid reactants. As with other dissociation expressions, the molar
concentration of the products is divided by the molar
concentration of the reactants. Because water is a pure liquid with
a constant concentration, it is omitted.
The numerical value of the acid dissociation expression is the acid
dissociation constant.
For example, the acid dissociation expression for the equilibrium
equation of formic acid shown above is written
HCOOH + H2O HCOO- + H3O+

Ka = [H3O+][HCOO-]/[HCOOH]
The numerical value of the Ka for formic acid at 25 °C is
determined by experiment to be 1.8 * 10-4
 Ka
• The Ka for formic acid is small, which confirms that the
equilibrium mixture of formic acid in water contains
mostly reactants and only small amounts of the
products. (Recall that the brackets in the Ka represent
the molar concentrations of the reactants and products).
• Weak acids have small Ka values. However, strong acids,
which are essentially 100% dissociated, have very large
Ka values, but these values are not usually given.
• The table on next slide gives Ka and Kb values for
selected weak acids and bases.
Acids Formula Ka
Phosphoric acid H3PO4 7.5* 10-3
Nitrous acid HNO2 4.5*10-4
Hydrofluoric acid HF 3.5*10-4
Formic acid HCOOH 1.8* 10-4
Acetic acid CH3CHOOH 1.8*10-5
Carbonic acid H2CO3 4.3*10-7
Hydrosulfuric acid H2S 9.1*10-8
Dihydrogen phospahe H2PO4- 6.2*10-8
Hydrocyanic acid HCN 4.9*10-10
Hydrogen carbonate HCO3 5.6*10-11
Hydrogen phosphate HPO42- 2.2*10-13
Dissociation constant for bases(K ) b

• Let us now consider the dissociation of the weak

base methylamine:
CH3¬NH2(aq) + H2O(l) CH3¬NH3+(aq) + OH-(aq)
• As we did with the acid dissociation expression, the
concentration of water is omitted
• from the base dissociation expression, Kb. The base
dissociation constant for methylamine
• is written
• Kb =[CH3¬NH3+][OH-]/[CH3¬NH2] = 4.4 * 10-4
Bases Formula Kb
Methylamine CH3-NH2 4.4*10-4

Carbonate CO32- 2.2*10-4

Ammonia NH3 1.8*10-5

Characteristic Strong acid Weak Acid
Equilibrium To the right To the left
position (toward products) (toward reactants)

Ka Large Small
[H3O] & [A-] 100% HA Small percent of HA
dissociates dissociates
Conjugate base Weak Strong
Characteristics Strong Base Weak Base
Equilibrium To the right To the left(towards
position (toward products) reactants)

Kb Large Small
[BH+] & [OH-] 100% of B reacts Small percent of B reacts
Conjugate Acid weak strong
Exercise
1.Write the acid dissociation expression for the weak
acid nitrous acid.
Step1: Write balance equation
HNO2(aq) + H2O(l ) H3O+(aq) + NO2-(aq)
Step2: Write the concentrations of the products as the
numerator and the reactants as the denominator. The
acid dissociation expression is written as the
concentration of the products divided by the
concentration of the undissociated weak acid.
Ka =[H3O+][NO2-]/[HNO2]
Question2: Write the acid dissociation expression for
hydrogen phosphate (HPO42-).
Answer Ka =[H3O+][PO43-]/[(HPO42-]
Answer true or false for each of the following: A strong
acid
a. is completely dissociated in aqueous solution
b. has a small value of Ka
c. has a strong conjugate base
d. has a weak conjugate base
e. is slightly dissociated in aqueous solution
Question2: Answer true or false for each of the following:
A weak acid
a. is completely dissociated in aqueous solution
b. has a small value of Ka
c. has a strong conjugate base
d. has a weak conjugate base
e. is slightly dissociated in aqueous solution
Consider the following acids and their dissociation
constants:
H2SO3(aq) + H2O(l) H3O+(aq) + HSO3-(aq)
Ka = 1.2 * 10-2
HS- (aq) + H2O(l) H3O+(aq) + S2-(aq)
Ka = 1.3 * 10-19
a. Which is the stronger acid, H2SO3 or HS-?
b. What is the conjugate base of H2SO3?
c. Which acid has the weaker conjugate base?
d. Which acid has the stronger conjugate base?
e. Which acid produces more ions?
14.30 Consider the following acids and their
dissociation constants
Writing the Water Dissociation Expression, Kw
Using the equation for water at equilibrium, we can write
its equilibrium expression that
shows the concentrations of the products divided by the
concentrations of the reactants.
Recall that square brackets around the symbols indicate
their concentrations in moles per liter (M).
H2O(l ) + H2O(l ) H3O+(aq) + OH-(aq)

K = [H3O+][OH-]/[H2O][H2O]
By omitting the constant concentration of pure water, we
can write the water dissociation
expression, Kw.
Kw = [H3O+][OH-]
Experiments have determined, that in pure water,
the concentration of H3O+ and OH- are equal at
25 °C are each 1.0 * 10-7 M.
Pure water [H3O+] = [OH-] = 1.0 * 10-7 M
When we place the [H3O+] and [OH-] into the
water dissociation expression, we obtain
the numerical value of Kw, which is 1.0 * 10-14 at
25 °C.
As before, the concentration units are omitted in
the Kw value.
Kw = [H3O+][OH-]
= [1.0 * 10-7][1.0 * 10-7] = 1.0 * 10-14
Neutral, Acidic.& Basic Solution

Type [H3O+] [OH-] Kw

Neutral 1.0 * 10-7 1.0 * 10-7 1.0 * 10-14
Acidic 1.0 * 10-2 1.0 * 10-12 1.0 * 10-14
Basic 1.0 * 10-8 1.0 * 10-6 1.0 * 10-14
Using the Kw to Calculate [H3O+] and [OH−] in a
Solution
If we know the [H3O+] of a solution, we can use the
Kw to calculate the [OH-]. Similarly If we know the
[OH-] of a solution, we can calculate [H3O+] from
their relationship in the Kw,as shown below
Kw = [H3O+][OH-] ;
 [OH-] =Kw/[H3O+]
[H3O+] =Kw/[OH-]
Example: Calculate [H3O+] of vinegar solution
whose[OH-] of 5.0 * 10-12M at 250C
Answer; [H3O+] =Kw/[OH-] =1* 10-14/(5*10-12)
= 2.0 * 10-3 M
1.Why are the concentrations of H3O+ and
OH- equal in pure water?
2. What is the meaning and value of Kw at
25 °C?
3. In an acidic solution, how does the
concentration of H3O+ compare to the
concentration of OH-?
4. If a base is added to pure water, why
does the [H3O+] decrease?
5. Indicate whether each of the following
solutions is acidic,
5.Indicate whether each of the following solutions is
acidic,
basic, or neutral:
a. [H3O+] = 2.0 * 10-5 M
b. [H3O+] = 1.4 * 10-9 M
c. [OH-] = 8.0 * 10-3 M
d. [OH-] = 3.5 * 10-10 M
6.Calculate the [H3O+] of each aqueous solution with
the following [OH-]:
a. NaOH, 1.0 * 10-2 M
b. milk of magnesia, 1.0 * 10-5 M
c. aspirin, 1.8 * 10-11 M
d. seawater, 2.5 * 10-6 M
PH SCALE
PH = -log[H3O+]
Although we have expressed [H3O+] and [OH-]as molar
concentrations, it is more convenient to describe the
acidity of solutions using the pH scale. On this scale, a
number between 0 and 14 represents the[H3O+]
Concentration for common solutions. A neutral solution
has a pH of 7.0 at 25 °C. An acidic solution has a pH less
than 7.0; a basic solution has a pH greater than 7.0
Acidic solution pH < 7.0; [H3O+] >1.0 * 10-7 M
Neutral solution pH = 7.0 ;[H3O+] = 1.0 * 10-7 M
Basic solution pH> 7.0 ;[H3O+] < 1.0 * 10-7 M
Calculating the pH of Solutions
The pH scale is a logarithmic scale that corresponds
to the [H3O+] of aqueous solutions.
Mathematically, pH is the negative logarithm (base
10) of the [H3O+].
pH = -log[H3O+]
Essentially, the negative powers of 10 in the molar
concentrations are converted to positive
numbers. For example, a lemon juice solution with
[H3O+] = 1.0 * 10-2 M has a pH of
2.00. This can be calculated using the pH equation:
pH = -log[1.0 * 10-2]
pH = -(-2.00)
= 2.00
Exercise/Examples
Question 1.Aspirin, which is acetylsalicylic acid, was
the first nonsteroidal anti- inflammatory drug
(NSAID) used to alleviate pain and fever. If a solution
of aspirin has a [H3O+] = 1.7 * 10-3 M, what is the pH
of the solution?
PH = -log(= 1.7 * 10-3 ) = 2.77
Question2: What is the pH of bleach with [H3O+] =
4.2 * 10-12 M?
Answer; PH =-log(4.2 * 10-12 )= 11.38
pH = 11.38
Calculating PH from POH
When we need to calculate the pH from [OH-],
we use the Kw to calculate [H3O+],
place it in the pH equation, and calculate the pH
of the solution as shown in example below
Example 1: What is the pH of an ammonia
solution with [OH-] = 3.7 * 10-3 M?
Method 1: POH + PH = 14
PH = 14-POH
- -3
P OH = -log [OH ] = -log (3.7 * 10 ) = 2.4317
PH = 14-POH = 14-2.4317=11.568

Method 2: [H3O+] Kw/ [OH-] = 10-14 /( 3.7 * 10-3)

= 2.7 * 10-12
Example 2: Calculate the pH of a sample of bile
that has [OH-] = 1.3 * 10-6 M.
ANSWER
pH = 8.11
pOH
The pOH scale is similar to the pH scale except that pOH
is associated with the [OH-] of an aqueous solution.
pOH = -log[OH-]
Solutions with high [OH-] have low pOH values;
solutions with low [OH-] have high pOH values. In any
aqueous solution, the sum of the pH and pOH is equal
to 14.00, which is the negative logarithm of the Kw.
pH + pOH = 14.00
For example, if the pH of a solution is 3.50, the pOH can
be calculated as follows:
pH + pOH = 14.00
pOH = 14.00 - pH = 14.00 - 3.50 = 10.50
 Comparison of PH & POH ,[H3O],[OH-]
PH [H3O+] [OH-] POH
0 10^0(1) 10^-14 14
1 10^-1(10) 10^-13 13
2 10^-2(100) 10^-12 12
3 10^-3(1000) 10^-11 11
4 10^-4(10000) 10^-10 10
5
6
7 10^-7 10^-7 7
8 10^-8 10^-6 6
9
10 10^-10 10^-4 4
14 10^-14 10^0 1
Assignment
1.A solution with a pH of 3 is 10 times more acidic than a
solution with pH 4. Explain.
2. A solution with a pH of 10 is 100 times more basic
than a solution with pH 8. Explain.
3. Calculate the pH of each solution given the following:
a. [H3O+] = 1 * 10-4 M b. [H3O+] = 3 * 10-9 M
c. [OH-] = 1 * 10-5 M d. [OH-] = 2.5 * 10-11 M
e. [H3O+] = 6.7 * 10-8 M f. [OH-] = 8.2 * 10-4 M
4. Calculate the pOH of each solution given the
following:
a. [H3O+] = 1 * 10-8 M b. [H3O+] = 5 * 10-6 M
c. [OH-] = 1 * 10-2 M d. [OH-] = 8.0 * 10-3 M
e. [H3O+] = 4.7 * 10-2 M f. [OH-] = 3.9 * 10-6 M
5.A patient with severe metabolic acidosis has a
blood plasma pH of 6.92. What is the [H3O+] of
the blood plasma?
6 A patient with respiratory alkalosis has a
blood plasma pH of 7.58. What is the [H3O+] of
the blood plasma
 PH of strong Acid /Base
• Strong acid HA dissociate fully, a not usually
shown.
• Example: Calculate PH of (i)2M HCL (ii) 2M
sulfuric acid
Solution
HCL H+ + Cl-
Ratio 1 1 1
[HCL]= [H+ ] PH =-log [H+ ] = -log 2= -0.3010
• 2M H2SO4
• H2SO4 H+ + SO42-
• Ratio 1 2 1
• [H2SO4 ] : [H+ ] = 1:2
• [H+ ] = 2* [H2SO4 ] = 2*2M= 4m
• PH=-log 4=-o.6021
• Calculte PH of 2M NaOH & 2M Ca(OH)2
• NaOH Na+ + OH-
• Ratio 1 1 1
• [OH-]= [NaOH] ; POH -Log 2 = -0.3010
• PH = 14 –0.3010= 14.3010
• Ca(OH)2 Ca2+ + 2OH-
• [OH-] = 2*2 =4; POH -log4 =-0.6021
• PH= 14—0.6021= 14.6021
Reaction of Acids & Bases
Typical reactions of acids and bases include the
reactions of acids with metals, carbonates or
bicarbonates, and bases. For example, when you drop
an antacid tablet in water, the bicarbonate
ion and citric acid in the tablet react to produce
carbon dioxide bubbles, water, and
salt. A salt is an ionic compound that does not have
H+ as the cation or OH- as the anion.
Acids React with Carbonates or Bicarbonates
When an acid is added to a carbonate or bicarbonate,
the products are carbon dioxide gas,water, and a salt.
The acid reacts with CO32- or HCO3 - to produce
carbonic acid (H2CO3),which breaks down rapidly to CO2
and H2O.
2HCl(aq) + Na2CO3(aq) CO2(g) + H2O(l) + 2NaCl(aq)
Acid Carbonate Carbon Water Salt
dioxide
HBr(aq) + NaHCO3(aq CO2(g) + H2O(l ) + NaBr(aq)
Acid Bicarbonate Carbon Water Salt
dioxide
Acids and Hydroxides: Neutralization
Neutralization is a reaction between a strong or weak
acid with a strong
Acids and Hydroxides: Neutralization
Neutralization is a reaction between a strong or weak acid
with a strong base to produce water and a salt. The H+ of the
acid and the OH- of the base combine to form water. The salt
is the combination of the cation from the base and the anion
from the acid. We can write the following equation for the
neutralization reaction between HCl and NaOH:
HCl(aq) + NaOH(aq) H2O(l ) + NaCl(aq)
Acid Base Water Salt
If we write the strong acid HCl and the strong base NaOH as
ions, we see that H+ combines
with OH- to form water, leaving the ions Na+ and Cl- in
solution.
H+(aq) + Cl-(aq) + Na+(aq) + OH-(aq) H2O(l ) + Na+(aq) + Cl-
(aq)
Antacids
Antacids are substances used to neutralize excess
stomach acid (HCl). Some antacids are mixtures of
aluminum hydroxide and magnesium hydroxide. These
hydroxides are not very soluble in water, so the levels of
available OH- are not damaging to the intestinal tract.
However, aluminum hydroxide has the side effects of
producing constipation and binding phosphate in the
intestinal tract, which may cause weakness and loss of
appetite. Magnesium hydroxide has a laxative effect. These
side effects are less likely when a combination of the
antacids is used.
Al(OH)3(s) + 3HCl(aq) 3H2O(l) + AlCl3(aq)
Mg(OH)2(s) + 2HCl(aq) 2H2O(l) + MgCl2(aq)
Antacids neutralize excess stomach acids. About 10% of the
calcium is absorbed into the bloodstream, where it elevates
the level of serum calcium. Calcium carbonate is not
recommended for patients who have peptic ulcers or a
tendency to form kidney stones, which typically consist of
an insoluble calcium salt.
CaCO3(s) + 2HCl(aq) CO2(g) + H2O(l ) + CaCl2(aq)
Still other antacids contain sodium bicarbonate. This type of
antacid neutralizes excess gastric acid, increases blood pH,
but also elevates sodium levels in the body fluids. It also is
not recommended in the treatment of peptic ulcers.
NaHCO3(s) + HCl(aq) CO2(g) + H2O(l) + NaCl(aq)
The neutralizing substances in some antacid preparations
are given in table on next next slide.
Antacids Bases
Amphogel Al(OH)3
Milk of magnesia Mg(OH)2
Mylanta,Maalox Mg(OH)2,Al(OH)3
Bisodol CaCO3,Mg(OH)2
Tums CaCO3
Alka-Shetzer NaHCO3,KHCO3
• Each of this theory has advantages and
disadvantages depending on the solvent or
medium being used
• The Lowry- Bronsted theory will be used. It
describes an acid as a proton donor and a
base as proton acceptor and the preferred
solvent is water since it is a constituent of the
body system.
Acid -base serves two distinct roles in
pharmaceutical preparation as;
1. Acid-base reaction that are employed in
pharmaceutical procedures. These include
i. Use of conjugate pairs as buffers
ii. Neutralization reaction in analytical and
preparative procedures
iii. Specialized acid base system of effervescent
mixtures
2. The use of acid and bases as therapeutic
agent in the control and adjustment of the
PH of GIT,body fluid and urine
 Neutralization procedure in pharmacy

• Neutralization reaction is the reaction

between acid and bases to form a product. It
may involve transfer of a proton to a base to
form conjugate pairs as the product
• Acid + Salt Salt + water
• HCL + NaoH NaCl + H2O
 Criteria for selection of base/acid
• When neutralization procedure is desired, the following
theoretical and practical factors is considered;
• Acid base strength of the member of the reacting
conjugate pairs
• Acid base properties of the solvent
• The extend of neutralization required as it determine
the choice of neutralizing agents
• Handling and storage
• Possible incompatibilities
• It is advantageous to have water/carbonic acid
as by product of neutralization. Why ?
• Water become part of the solvent while
carbonic acid At high temperature evaporates
to the atmosphere as carbon dioxide
 Bases of choice
• There are three bases most frequently selected
in pharmaceutical practice namely;
• Hydroxyl ion (OH-)
• Bicarbonate (HCO3-)
• carbonate (CO32-) usually in the form of sodium
salts. Potassium is rarely used, sodium is
preferred because of physiological compatibility,
and also the solubility it imparts to its compound
is critical
 Acids of choice
• The acids of choice for pharmaceutical use are
hydrochloric acid (HCL),sulphuric
acid(H2SO4),phosphoric acid(H3PO4),organic
acids(acetic ,tartaric ,citric acids)
• Each of this acid has advantages and
disadvantages
Survey specific neutralization application
 Application
Acids bases are generally used in pharmaceutical practice to
1. Neutralization of acid or bases whichever is applicable .examples
 NaHCO3 in ascorbic acid injection
 Acetic acid in preparation of aluminium subacetate
 HCL in lignocaine
2. Stability improvement of medicinal as it provides optimum PH
conditions. Example addition of NaHCO3 to solution of NaOCl to
reduce its PH from 12 to 7,8 which is optimal for germicidal
activity. Citric acid is included in ephedrine sulphate provide a
stabilizing syrup media
3. Solubility control during extraction 
BUFFERS AND THEIR ROLE IN THE PRACTICE OF PHARMACY

• Definition & mechanism of action

• Buffer system may be defined on the basis of
its constituent as an aqueous solution of a
bronsted acid and its conjugate base
• Buffers system may be defined on the basis of
its properties as solutions which has a capacity
for neutralization of added acids/bases with
minimum shift in PH
• Solutions composed of weak acids and one of
its salts e.g. CH3COOH + CH3COONa or
CH3COONH4
• Weak base and one of its salts(e.g. NH4OH +
NH4CL)
 Types of buffers
1.On the basis of chemical nature
• Acidic buffers: weak acid & its corresponding salts e.g.
CH3COOH /CH3COONa
• Basic buffers : Weak base & its salts e.g NH4OH/NH4CL
• Neutral buffer: Single substance showing properties of
buffers e. Ammonium acetate
2.On the basis of use
 Analytical buffers
 Pharmaceutical buffers
 Henderson- Hasselbach equation
• It relates the PH of an aqueous solution of an
acid to the acid dissociation constant(Ka)
• Consider weak acid HA which dissociates;
• HA H+ + A-
• Ka = [H+]*[A-]/[HA]; take log on both sides
• Log Ka= Log{+]*[A-]/[HA} Note;
• LogA/B= logA-Log B; Log AB= Log A+LogB
• Log Ka= Log{[H+]*[A-]/[HA}
• = Log{[H+] +log{[A-]/[HA} Multiply both
sides by (-1)
• -Log Ka = - Log{[H+] - log{[A-]/[HA}
• Note: - Log{[H+] = PH & -Log Ka = pKa
• pKa= PH - log{[A-]/[HA}
• PH= pKa + log{[A-]/[HA}
• PH= pKa + log{[A-]/[HA}
• OR PH= pKa + log[Ionized]/[Unionized}
• OR PH= pKa + log[Base]/[Acid]
• OR PH= pKa + log[Dissociated]/[Undisocciated]
• These equations are referred to as Henderson-
Hasselbach equation for a weak acid
 Henderson- Hasselbach equation
• Consider weak Base B
• B + H2O BH+ + OH-
• Or BOH B+ + OH-
• Kb = [B+][OH-]/BOH Take log both sides
• LogKb= log[B+][OH-]/[BOH]
= log[OH-] + log[B+]/[BOH] (*-1 )
-Log Kb= -log[OH-] - log[B+]/[BOH]
• -Log Kb= -log[OH-] - log [B+]/[BOH]
• Note ; -Log Kb= pKb; log[OH-] = pOH
• Hence; pKb= pOH -Log [B+]/[BOH]
• Note: pH + POH =14; pOH=14-pH
• Substituting
• pKb=(14-pH) - Log [B+]/[BOH]
• Note: Pka + pKb= 14,pKb= 14-Pka
• pKb=(14-pH) - Log [B+]/[BOH]
• Note: Pka + pKb= 14,pKb= 14-Pka
• Substituting
• 14-pKa = 14-pH - Log [B+]/[BOH]
• pH= pKa - Log [B+]/[BOH]
• Or PH = pKa- log [ionized]/[Unionized]
• These equations are referred to as Henderson-
Hasselbach (HH)equation for a weak base
Example 1.What is the pH of a buffer prepared by
dissolving 25.0 g ofK2HPO4and 25.0 g ofKH2PO4in 250
mL of water?
Solution. First, we determine which species is the weak
acid and which is the conjugate weak base. Both
compounds are ionic and will dissociate in water. The K+
ions have no effect on the solution’s pH, so we ignore
them. The remaining anions are amphiprotic, meaning
they have both acidic and basic properties. Because
dihydrogen phosphate has one more proton than
monohydrogen phosphate,H2PO4–, is the weak acid.
•To find the pH of the resulting buffer, we find the initial
moles of weak acid 25.0g KH2PO4( RMW= 136.5)
[KH2PO4 ]= {weight/Rmw} =25/136.5 = 0.1837 moles
•Concentration of weak Base25.0g K2HPO4 ( RMW
174.2) Moles of [HPO42–]= Mass/RMW= 25/174.2=
0.1435mol
•Although the recipe contains information on the amount
of water used to prepare the buffer, we don’t need to
include this in our calculation ,since it is equal in both
base & acid.
•Knowing the moles ofH2PO4–
andHPO42–, we complete the calculation
using the pKa( value for H2PO4–; thus
•PH= pKa + log{[A-]/[HA}
= 7.2 + log {0.1435/0.1837}
=7.2-0.10725= 7.0927
 QUESTION
• Derive the Henderson-Hasselbalch equation
for a weak acid ,HA 4marks
• Calculate the PH of 0.05M sodium acetate,
given that Pka of acetic acid is 4.66 4marks
• Calculate the pH of 0.05M sodium acetate solution if the pKa​ of acetic acid is 4.74.
• Answer
• CH3​COO− ion of CH3​COONa hydrolysis in water as

• 1(1−h)CH3​COO−​+H2​O⇋0hCH3​COOH​+0hOH−​

• where h is degree of hydrolysis of CH3​COONa. Also pKa=4.74 and thus −logKa​=4.74 or Ka​

=1.82×10−5

• [OH−]=c.h=c.cKh​​=Ka​Kw​.c​​=1.82×10−510−14×0.05​​=5.24×10−6

• ∴pOH=−log[OH−]=−log5.24×10−6=5.2805;pH=14−pOH=14−5.2805=8.7195
 QUESTION
Using Henderson-Hasselbalch equation:
pH = pKa + log [salt]
[Acid]
Calculate the pH of buffer solution made by
mixing together 100 cm3 of 0.100M ethanoic
acid and 50 cm3 of 0.400M sodium ethanoate,
given that Ka for ethanoic acid is 1.74 x 10-
5
 mol dm-3 (5 marks)
 Buffer capacity(β)
• It is defined as moles of strong acid or base ,in grams
equivalent required to change the PH of 1Litre of solution by
1 unit. It is unit less
• It is a measure of efficiency of a buffer in resisting change in
PH
• More concentrated buffers have a higher capacity, as they
have more molecules that can interact with additional acids
or bases
• β = n/ ΔpH where β is buffer capacity
• n=number of moles of base /acid added;
• ∆PH is change in PH
The term "buffer capacity" (β) quantifies the change in
pH of the solution caused by the addition of a strong acid
or base. It is calculated in relation to 1 dm3 of a buffer
solution. β≈|Δn/ΔpH|
β – buffer capacity,
Δn – amount of added acid/base to the buffer
solution [mol],
ΔpH – pH change cause by the addition of
acid/base.
The value of the buffer capacity is strongly related
to the concentrations of ingredients used and
increases with their increase.
-Buffer solutions with a pH equal to the
pKa value of the acid (used to make this
solution) have the greatest buffering
capacity.
• The capacity to resist shift in PH is governed
by factors which can be derived from
Henderson Hasselbach equation
• PH = Pka + Log[Base]/[Acid]
• Concentration of each constituent [Base/Acid]
• The ratio of the constituent
• The Pka of the buffer acid
• The strength of the added acid
 Mechanism of action

Buffer is composed of weak acids and its salt or

weak base and its salt ; e.g.
• CH3COOH /CH3COONa
i. CH3COOH CH3COO- + H+ ( Left)
ii. CH3COONa CH3COO- + Na+ (Right)
In (i) there are large quantities of CH3COOH
because equilibrium lies to left(Weak acid)
In (ii) there are large quantities of CH3COO-
because equilibrium lies to the right(strong
base)
• Addition of H+; reacts with excess CH3COO-
• CH3COO- H+ CH3COOH
• Addition of OH; reacts with excess CH3COOH
to form CH3CHOONa
• CH3COOH + OH- CH3COONa + H2O
 Effective Buffer range

• Buffers are characterized by the pH range over which

they can maintain a more or less constant pH and by
their buffer capacity, the amount of strong acid or base
that can be absorbed before the pH changes significantly.
Although the useful pH range of a buffer depends
strongly on the chemical properties of the weak acid and
weak base used to prepare the buffer (i.e., on K), its
buffer capacity depends solely on the concentrations of
the species in the buffered solution. The more
concentrated the buffer solution, the greater its buffer
capacity
Properties of buffers
1. The pH of buffer solution is constant.
2. The pH does not change with dilution.
3. The pH does not change with even after
addition of small quantities of acid or
bases
Factors to consider in selection of buffers
A. Chemical factors
B. Pharmaceutical factors
A. Chemical factors:
1.Thebuffer system should not react with other
chemicals in the preparation.
2.It should have reasonable chemical stability.
3.Buffer capacity depends on absolute
concentration of each buffer compound
 Selection of buffers
Chemical Factors
• Factors to consider in selection of buffers
• PH=Pka + log [base]/[acid]
• Pka
• Log ratio
• Concentration
• Chemical stability
 Common buffers in pharmacy
• Phosphate buffer
• Borate buffer
• Organic buffers; tartarate, citrate,acetate
Pharmaceutical factors:
1.Toxicity of buffers :some of the buffers have limited
use in the pharmaceutical practice because of there
toxicity.
2.Effect on pharmaceutical actions of the preparation:
buffer system should not interact with the action of
ingredient of preparation.
3.Contamination by microorganism: many buffers
system support the microbial growth as they can serve
as nutrient media for moulds when their PH is at
neutrality
 Role of buffers in pharmacy
1. Stability of compounds
2. Optimizing biological activity
3. Solubility
4. Patient comfort
5. Colour
6. Analytical work in the laboratory
Role of Buffers
1. Optimizing biological activity: The buffers are
employed in pharmaceutical preparation to
ensure the maintenance of optimum pH
conditions for activity of medicinal compounds.
2. Solubility of many compounds is controlled by
providing suitable pH . For example in acidic
medium, solubility of different compounds
(Inorganic salts of Fe3+,phosphates and borates)
is increased, but this inorganic salts precipitate in
alkaline media
3. Color of many compounds is pH dependent. The
PH of a solution is known affect the colour of
many natural dyes present in fluid extracts or
synthetic drug
4. Stability of compounds: Because of
hydrolysis, many compounds are unstable in
aqueous solutions. These solutions are
stabilized by regulating the PH. pH gives
stability to different preparations.
 Penicillin is more stable at PH range (5.0-
8.0) ,maximum stability is at PH 6.0.Instability
is much higher at acidic values than basic PH
values.
 Sodium thiosulphate and sodium
polysulphide preparation are stored in
alkaline conditions to prevent separation of
-sulphur.Salts of carbonates and sulphites at
acidic medium liberates carbon dioxide and
sulphur respectively,hence should be stored in
basic medium.
5. It provides patient comfort. Mainly concerns
injectables and opthalmics. preparations
become irritating if their PH is different from
the normal for the particular tissue involved.
In case of parenteral preparation,buffers are
generally used to maintain PH with
physiological range of lacrimal fluid(eye fluid-
PH7.8).Buffering agents include
borate ,carbonate & phosphates
 Topical products such as ointment and cream
are also buffered for stability. The most
common used buffer in ointments and cream
are citric acid/its salts, phosphoric acids /its
salts
6. Control work/Analytical laboratory : it is
frequently necessary to prepare buffers of
known PH for use as standards in calibration.
Calibration of PH meter and preparation of
indicator colour standards need accurate
known buffer solutions
 Role of buffers in pharmacy
1.Stabilization of medicinal
a) Assure stable conditions for medicinally active
compounds. Solubility is often controlled by
providing media .Many inorganic salts e.g.Fe3+,
phosphate, borates are soluble in acidic media and
precipitate in alkaline media. Amines are also soluble
in acidic media but almost insoluble in alkaline
media
b) ensuring color of dye present in pharmaceutical
c) control of oxidation
2. Patient comfort : mainly concern injectables and
ophthalmics
3. Provision of optimal activity of medicinal : Buffers
provide optimum conditions for activity of
medicinal. Adjustment of PH of NaOCl to lower
value by use of NaHCO3 increase germicidal activity
4. Control work : it is frequently necessary to prepare
buffers of known PH for use as standards in
calibration
 Physiological buffers
1. Carbonic acid/bicarbonate buffer : Most
important buffer in ECF.
CO2 + H2O = H2CO3= H+ + HCO3-
2. Phosphate buffer: Buffer of ICF and urine
3. Protein buffers-help regulate PH in ECF and
ICF . They interact extensively with other
buffer systems
Importance of physiological buffers
• Cells and organisms maintain a specific and
constant cytosolic PH,keeping biomolecules in
their optimal ionic state, usually PH 7.
• In multicellular organism, the PH of
extracellular fluid is also tightly regulated
• Constancy of PH is achieved primarily by
biological buffers, mixtures of weak acids and
their conjugate bases
The Carbonic-Acid-Bicarbonate Buffer in the Blood
By far the most important buffer for maintaining acid-
base balance in the blood is the carbonic-acid-
bicarbonate.It is the only important ECF buffer.
The simultaneous equilibrium reactions of interest
are
H+ + HCO3- H2CO3 H2O + CO2
We are interested in the change in the pH of the
blood; therefore, we want an expression for the
concentration of H+ in terms of an equilibrium
constant and the concentrations of the other species
in the reaction (HCO3-, H2CO3, and CO2).
Phosphate buffer system:
Dihydrogen phosphate/monohydrogen
phosphate conjugate pair (pKa = 7.2)
H2PO4-1 is the weak acid, and HPO4-2 is the
conjugate base.
Sodium salts of dihydrogen phosphate
(H2PO4-1)- is a weak acid while
Monohydrogen phosphate(HPO4-2 )- weak
base
(These two provided by filtration)
It is an effective buffer in urine &
PROTEINS BUFFER SYSTEM
Plasma and intracellular proteins are the body’s most
plentiful and powerful buffers.
Amino acids are the building blocks of proteins. They
are organic molecule with at least one CARBOXYL
group (organic acid) and at least one AMINO group
(organic base)
- Amino acids act as: enzymes (catalysts), metabolic
intermediates, carriers of energy and waste products
and hormones. -
At physiological pH (~7.4), amino acids exist as
zwitterions – positive and negative charge on the same
molecule. Dependent upon the pKa of the group. For
example
General anatomy of an amino acid.
Except for proline and its derivatives, all
of the amino acids commonly found in
proteins possess this type of structure.
Have both ACID and BASE groups in same
molecule
Proteins are Amphoteric molecules i.e.
function as both weak acid and weak
bases