Analytical Chemistry

Lecture 3
Acid-Base, pH and Buffer

Instructor: Nguyen Thao Trang

School of Biotechnology
Semester I 2017-2018
Acid-Base Definition
Definition of Arrehnius (Sweden, 1884):
Acid:
Acid is a substance that can release proton or hydrogen ion when
dissolved in water.

HCl H+ + Cl-
Must have H in formula. The general formula is HnX.
Monoprotic: one acidic proton
HNO3 Nitric acid

HCl Hydrochloric acid

HBr Hydrobromic acid

CH3COOH Acetic acid

2
Acid-Base Definition
Definition of Arrehnius (Sweden, 1884):
Acid:
Diprotic: two acidic protons
H2SO4 Sulfuric acid
H2SO3 Sulfurous acid
Triprotic: three acidic protons
H3PO4 Orthophosphoric acid (Phosphoric acid)

Base:
Any substance that dissociates in H2O to give OH- ions.
NaOH Na+ + OH-
The general formula is M(OH)n: NaOH, KOH, Ca(OH)2, Mg(OH)2,
Al(OH)3

3
Acid-Base Definition
Definition of Arrehnius (Sweden, 1884):
Strength of Acid/Base:
Acids and bases are commonly classified as strong or weak, depending
on whether they react nearly completely or only partially to
produce H+ or OH-.

Example:
In a 6 M solution of HCl, 99.996% HCl molecules reacts with water to form
H+ and Cl- HCl is a strong acid.

Acetic acid is a weak acid as 1% CH3COOH reacts with water to form H3O+
and CH3COO- CH3COOH is a weak acid.

Equilibrium constant or dissociation constant Ka (acid) or Kb (base)

reveals if an acid/base is strong or weak.

4
Acid-Base Definition
Definition of Arrehnius (Sweden, 1884):
Strength of Acid/Base:
Example:

CH3COOH (aq) = CH3COO- (aq) + H+ (aq)

[CH3COO-] [H+]
Ka =
[CH3COOH]

= 1.76 x 10-5

pKa ( = negative of log10 Ka) can also be used:

pKa = - log10 (1.76 x 10-5) = 4.75

5
Acid-Base Definition
Definition of Arrehnius (Sweden, 1884):
Strength of Acid/Base:
Example:

NH4OH (aq) = NH4+ (aq) + OH- (aq)

[NH4+] [OH-]
Kb =
[NH4OH]

= 1.76 x 10-5

pKb ( = negative of log10 Kb) can also be used:

pKb = - log10 (1.76 x 10-5) = 4.75

6
Acid-Base Definition
Definition of Arrehnius (Sweden, 1884):
Strength of Acid/Base:
stronger
The stronger the acid, the larger the Ka (the smaller the pKa):

HNO2 (aq) = NO2- (aq) + H+ (aq) Ka = 4.6 x 10-4

pKa = 3.34

CH3COOH (aq) = CH3COO- (aq) + H+ (aq) Ka = 1.76 x 10-5

pKa = 4.75

HCN (aq) = CN- (aq) + H+ (aq) Ka = 6.17 x 10-10

pKa = 9.21
weaker 7
Acid-Base Definition

8
Acid-Base Definition

9
Acid-Base Definition
Definition of Arrehnius (Sweden, 1884):
Strength of Acid/Base:
The stronger the base, the larger the Kb (the smaller the pKb):
stronger

PO43- (aq) + H2O (l) = HPO42- (aq) + OH- (aq) Kb = 4.5 x 10-2
pKb = 1.34

NH4OH (aq) = NH4+ (aq) + OH- (aq) Kb = 1.8 x 10-5

pKb = 4.74

weaker
10
Acid-Base Definition
Definition of Arrehnius (Sweden, 1884):
Strength of Polyprotic Acid/Base:
Example: oxalic acid is diprotic and phosphate is tribasic:

Ka1 (or K1) refers to the acidic species with

the most protons.
Kb1 refers to the basic species with the least
number of protons.
11
Acid-Base Definition
Definition of Arrehnius (Sweden, 1884):
Strength of Polyprotic Acid/Base:

12
Acid-Base Definition
Definition of Arrehnius (Sweden, 1884):
Limitations:
Many substances dissolve in water to give acidic or basic solutions but
do not have the classical acid or base formulas.

Example: A solution of K2O in H2O is identical with a solution of KOH in

H2O. However , according to the Arrhenius system K2O cannot be
classified as a base in that it does not have OH-s in its formula.

13
Acid-Base definition
Definition of Lowry (England) or Bronsted working
independently in 1923 (Bronsted-Lowry definition):
Acid is a material that donates a proton.

HCl H+ + Cl-
NH4+ NH3 + H+
Base is a substance that accepts a proton.

OH- + H+ H2O
NH3 + H+ NH4+
The Bronsted Lowry definition can be extended to gas or nonaqueous
solvent:

14
Acid-Base definition
Bronsted-Lowry definition:
Acid: must have a H in its formula.
Base: must have a lone pair of electrons to form a covalent bond with
H+

NH4+ NH3 + H+
(Acid) (Conjugate base)

The product formed when an acid gives up a proton is a potential

proton acceptor and is called the conjugate base of the parent acid.

NH3 + H+ NH4+
(Base) (Conjugate acid)
The product formed when a base accepts a proton is a potential
proton donator and is called the conjugate acid of the parent base.
NH4+/NH3: a conjugate acid/base pair.
15
Acid-Base definition
Bronsted-Lowry definition:
General:

Combination of 2 reactions: neutralization reaction

Direction of the reaction depends on which acid donates proton stronger

or which base accepts proton stronger.

Example:

16
Acid-Base definition
Bronsted-Lowry definition:
Proton H+ does not exist by itself in water. It exists in the form of H3O+
(a proton covalently binds to a water molecule).
H5O2+ cation is another simple species.

Hydroxyl ion OH- also exists in the form of H3O2- (OH-.H2O)

17
Acid-Base definition
Bronsted-Lowry definition:
Species possess both acidic and basic properties: amphiprotic.
Example:
H2PO4- acts as a base:

H2PO4- acts as an acid:

Amino acids are amphiprotic compounds: rearrange to form

zwitterionic species that bears both a positive and a negative charge.

H2O, methanol, ethanol are common amphiprotic solvent.

18
Acid-Base definition
Bronsted-Lowry definition:
Autoprotolysis: self-ionization (autoionization) to form a pair of ionic
species

The extent of these reactions is very small. The autoprotolysis constant

(equilibrium constants) for H3O+/OH- pair is 110-14 M at 25oC.

19
Acid-Base definition
Bronsted-Lowry definition:
Autoprotolysis constant for H2O has the special symbol Kw

Kw = 1.01 10-14 or pKw = 14

Kw depends on temperature

20
pH
An approximate definition of pH is the negative logarithm of
the H concentration.

Relationship between pH and Kw

21
Acidity/basicity of a solution
Solution is acidic if [H+] > [OH-].

Solution is basic if [H+] < [OH-].

At 25oC, an acidic solution has a pH below 7 and a basic

solution has a pH above 7.

pH generally falls in the range 0 to 14, these are not the limits
of pH.

22
Acidity/basicity of a solution
What is pH of pure water?

If x = the molarity of [H+] ,

H2O = H+ + OH- Kw = [H+] [OH-] = 10-14

x x x2 = 10-14

Therefore, x = [H+] = [OH-] = 10-7 M in pure water at 25C.

23
Acidity/basicity of a solution
The degree of acidity or basicity of a solution is measured on
the pH scale

[H+] pH pOH
1 M 0 14 low pH or high pOH is strongly acid
10-2 M 2 12
10-4 M 4 10
10-6 M 6 8
pH 7 is a neutral solution
10-8 M 8 6
10-10 M 10 4
10-12 M 12 2
10-14 M 14 0 high pH or low pOH is strongly base
24
Acidity/basicity of a solution

25
Acid-Base definition
Bronsted-Lowry definition:
Relative strength of acids/bases: Strong acids will yield weak conjugate
bases and weak acids will give strong conjugate bases.

26
Acid-Base definition
Bronsted-Lowry definition:
Relationship between Ka and Kb for a conjugate acid/base pair:

For a diprotic acid or triprotic acid:

27
Acid-Base definition
Definition of J.N. Lewis:
Acid is a substance that accepts an electron pair in forming a
coordinate covalent bond.

A Lewis acid must have a fairly low energy vacant, or easily vacated
orbital.

Example:
BF3 (vacant 2p orbital on B)
Ni2+(vacant 3d, 4s, and 4p orbitals)
SO3 (the SO bond is easily broken)

Acid are electrophiles because they react readily with electron pair
donors.

28
Acid-Base definition
Definition of J.N. Lewis:
Base is a substance that donates an electron pair in forming a
coordinate covalent bond.
A Lewis base must have a lone pair of electrons the same as a
Bronsted-Lowry base.
Example:
H
.. .. 2-
.. .. :S :
- : N-H : O-H ..
: O-H
.. : :
..I
H H

hydroxide iodide ammonia water sulfide

The base is a nucleophile.

29
Acid-Base definition
Definition of J.N. Lewis:
The Lewis definition generalizes the acid/base concept:
Every Arrhenius acid/base is also a Lewis acid/base.
Every Bronsted acid/base is also a Lewis acid/base.

Least general definition Most general definition

Arrhenius Bronsted-Lowry Lewis

Example: A strong acid reacts with a strong base

H+(aq) + :OH-(aq) = H2O(l)

Electron pair acceptor electron pair donor

30
Acid-Base definition
Definition of J.N. Lewis:
A Lewis acid and base can interact by sharing an electron pair.
Example:
Formation of hydronium ion

O H +
+ H O H
H
H
H
ACID BASE

Involves metal ion:

O H
2+ Co
2+
O H
Co
H
H
ACID BASE

31
Buffers
A buffered solution resists changes in pH when acids or bases are added or
when dilution occurs.
Buffer is a mixture of an acid and its conjugate base such as acetic
acid/sodium acetate or ammonium chloride/ammonia.
pH of a weak acid (HA)/conjugate base (A-)buffer:

CHA and CNaA are analytical concentration of the acid HA and conjugate base A-
solutions.
At equilibrium:

32
Buffers

33
Buffers
Henderson-Hasselbalch Equation is used to calculate the pH
of buffer solutions:

For a weak acid and its conjugate base:

For a weak base and its conjugate acid:

34
Buffers
Use of the Henderson-Hasselbalch Equation
In most practical cases, the pH of the solution is known either from:

(1) direct measurement with a pH meter

(2) use of a pH buffer in the solution
When the pH is known, the H.-H. equation is much more convenient
to use than the equilibrium constant expression. It immediately gives
the ratio of concentrations of all conjugate acid/base pairs in the
solution.

Henderson-Hasselbalch
Equation

measured or known (from calculate ratio of

set by buffer tabulations) (base/acid) concentrations
35
Buffers

36
Buffers
pKa and the Dissociation of Weak Acids

For any conjugate acid/base pair:

If [A-] = [HA] then:

37
Buffers
pH, pKa and fraction of species in solution:

(F: analytical concentration of acid HA)

Fraction of HA (protonated form):

Fraction of A- (deprotonated from):

When pH = pKa: HA = A-

When pH < pKa: HA > A- : mostly protonated

When pH > pKa: HA < A- : mostly deprotonated 38

Buffers
pH, pKa and fraction of species in solution:

Example: Acetic acid CH3COOH

CH3COOH = H+ + CH3COO-

mostly Mostly
CH3COOH pKa=4.75 CH3COO-

0 7 14
pH
When pH = pKa= 4.75 : [CH3COOH] = [CH3COO-]

When pH < 4.75: CH3COOH is the dominant form

When pH > 4.75: CH3COO- is the dominant form

39
Buffers
pH, pKa and fraction of species in solution:
Example: A 0.050 M acetic acid solution is made pH 7.00 with added
NAOH. Determine [CH3COOH], [CH 3COO -], and [H+] in this solution.
pKa = 4.75
Determine [H+]:
pH = - log[H+] = 7 [H+]= 10-7 M

% %
[ CH3COO ] [CH3COO ]
= 7 4.75 = 2.25 = 102.25 = 178
CH3COOH CH 3COOH
CH3COO / = 178 CH3 COOH
As CH3COO / + CH3 COOH = 0.050 CH3COO / 0.050
CH3 COOH 2.810/8
2.810/8 x 100%/0.050 = 0.56% undissociated species
40
Diprotic buffers
Buffer made from a diprotic (or polyprotic) acid is treated in
the same way as a buffer made from a monoprotic acid.
For the acid H2A, either Henderson-Hasselbalch equations can
be used:

or

Major species in diprotic buffer:

41
Diprotic buffers
Example: Diprotic Weak Acid - H2CO3
H2CO3 = H+ + HCO3- pKa1 = 6.4
HCO3- = H+ + CO32- pKa2 = 10.3

pKa1=6.4 pKa2=10.3
mostly mostly mostly
H2CO3 HCO3- CO32-

0 7 14
pH

42
Triprotic buffers
Example: Triprotic Weak Acid H3PO4

H3PO4 = H+ + H2PO4- pKa1 = 2.12

H2PO4- = H+ + HPO42- pKa2 = 7.21
HPO42- = H+ + PO43- pKa3 = 12.67

pKa1=2.12 pKa2=7.21 pKa3=12.67

mostly mostly mostly mostly
H3PO4 H2PO4- HPO42- PO43-

0 7 14
pH
43
Buffer
Exercise:
Calculate the pH of a 500 mL solution prepared from 0.050 mole of
acetic acid and 0.020 mole sodium acetate.

HAc = H+ + Ac- pKa = 4.75

Henderson-Hasselbalch equations

/ =

pH =

44
Buffer
Exercise:
Suppose that 0.010 mol NaOH is added to the previous buffer. What is
the pH?
HAc = H+ + Ac- pKa = 4.75

Henderson-Hasselbalch equations:

/ =

pH =
Compare to the pH calculated in the previous part:
45
Properties of buffers
Effect of dilution:
The pH of a buffer solution remains essentially independent of dilution

Figure. The effect of dilution of the pH of

buffered and unbuffered solutions. The
dissociation constant for HA is 1.00 10-4.
Initial solute concentrations are 1.00 M

The dilution independence of the pH of a buffer solution becomes

invalid when the molar concentration of either the acid or its
conjugate base (or both) is very small.
46
Properties of buffers
Effect of added acid or base:
pH of a buffer solution resists to pH change after addition of small
amounts of strong acids or bases.

Example: calculate the pH change that takes place when a 100-mL portion of
(a) 0.0500 M NaOH and (b) 0.0500 M HCl is added to 400 mL of the buffer
solution that is composed of 0.200 M in NH3 and 0.300 M inNH4Cl

47
Buffer
Buffer capacity: measures how well a solution resists changes
in pH when acid or base is added.

Buffer capacity: defined as the number of moles of a strong

acid or a strong base that causes 1.00 L of the buffer to
undergo a 1.00-unit change in pH.

@ and B are the number of

@ B moles per liter of strong base and
= =
strong acid added to the buffer
respectively.

The greater the buffer capacity, the less the pH changes.

48
Buffer
Capacity of a buffer depends not only on the total
concentration of the two buffer components but also on their
concentration ratio.
Example (total concentration): soln A : 5.00 M HOAc + 5.00 M
NaOAc; soln B : 0.05 M HOAc + 0.05 M NaOAc; pH change when
0.01 mol of HCl(g) is added ?

A: % change: 0.4%

[A ]

=
5.00
= 1
+ 0.01 mol H +[A
] =
4.99
= 0.996
[HA] 5.00 [HA] 5.01
B:
[A ]

=
0.05
= 1
+ 0.01 mol H +[A
] =
0.04
= 0.67
[HA] 0.05 [HA] 0.06
% change: 37% 49
Buffer
Capacity of a buffer depends not only on the total
concentration of the two buffer components but also on their
concentration ratio.
Example (concentration ratio): soln A : 1.00 M HOAc + 1.00 M
NaOAc; soln B : 1.00 M HOAc + 0.01 M NaOAc; pH change when
0.01 mol of HCl(g) is added?

C: 2%
[A ]

=
1.00
= 1.00
0.01 mol H [A
] +
= 0.98
[HA] 1.00 [HA]
[A ]

=
1.00
= 100
0.01 mol H [A
]
+
= 49.5
[HA] 0.01 [HA]
original soln 50.5% new soln 50
Buffer
Capacity of a buffer is maximum when concentration of the
two buffer components are equal ( / = ).

/
CD

Buffer solutions should contain roughly equal concentrations of a

conjugate acid and its conjugate base.

The conjugate acid/base pair of the buffer should have a pKa that
approximately equals the pH (or within 1 unit of desired pH).
51
Buffer
Example: a buffer will result from mixing 0.1 M acetic acid and
0.1 M sodium acetate.
Acid: Acetic acid

Conjugate base: Sodium acetate

Equal concentration of acetic acid and sodium acetate results in

maximum buffer capacity.

Added OH- is neutralized by the conjugate acid:

OH- + HC2 H3 O2 = H2O + C 2H3 O2-

Added H+ is neutralized by the conjugate base:

H+ + C2H3 O2- = HC2 H3O2

52
Buffer
Preparation of buffer
Buffer solution of any desired pH can be prepared by combining
calculated quantities of a suitable conjugate acid/base pair.
Example: preparing a buffer solution at pH 5.00 containing acetic acid
and sodium acetate.

E%
CD = 0.25
FE

E%
5.00 4.75 = 100.25 = 1.78
FE

Any solution with [sodium acetate]/[acetic acid] = 1.78, will form a buffer
at pH 5.00, such as: [sodium acetate] = 0.178 M; ]/[acetic acid] = 0.1 M

53
Buffer

54