Acids and bases.

Buffers

Brnsted-Lowry theory of acids and bases

Definitions:
An acid is a substance that A base is a substance that can
can donate a hydrogen ion accept a hydrogen ion (H+).
(H+).
Examples:
acid
HCl + H2O H3O+ + Cl-

base
NH3 + H2O NH4+ + OHammonia

H2SO4 + H2O H3O+ + HSO4-

CH3NH2 + H2O CH3NH3+ + OHaminomethane

HSO4- + H2O H3O+ + SO42CH3COOH + H2O CH3COO- + H3O+

ethanoic acid
(acetic acid)

acetate ion

methylammonium ion

Brnsted-Lowry theory of acids and bases

When an acid gives up its H+, the resulting anion is a base.
This base is called conjugate base.
Acid H+ + Conjugate base
HCl + H2O H3O+ + ClCH3COOH + H2O
acetic acid

conjugate base
H3O++ CH3COOacetate ion; conjugate base

An acid and its conjugate base form conjugate pair.

HCl/Cl- ;
CH3COOH /CH3COO-

Brnsted-Lowry theory of acids and bases

A base reacts by accepting H+. The species produced by
this reaction is its conjugate acid.
Base + H+ conjugate acid
NH3(aq) + H2O NH4+ + OHbase
conjugate acid
A base and its conjugate acid form conjugate pair.
NH3/NH4+.

Brnsted-Lowry theory of acids and bases

Substances that can either lose or gain a hydrogen ion are
amphoteric substances.
NH3(aq) + H2O NH4+(aq) + OH-(aq)
H+ donor
conjugate base
HCl + H2O Cl- + H3O+
H+ acceptor conjugate acid

Water acts as an acid when it donates hydrogen ions to

ammonia.
It acts as a base in its reaction with hydrogen chloride.
Water is an amphoteric substance.
5

Brnsted-Lowry theory of acids and bases

Strength of acids and bases.

strong acids and bases

weak acids and bases

Strong acids are acids that ionize completely in water HNO3,
HCl, H2SO4, HClO4.
HCl H+ + ClAcids that are partially ionized in water are weak acids.
HCN hydrocyanate
H2CO3 carbonic acid
H3PO4, HF, CH3COOH etc.
Most organic acids are weak acids. The only H atom that does ionize to
some degree is the one, bonded to the oxygen atom of the COOH group.
CH3COOH CH3COO- + H+
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Brnsted-Lowry theory of acids and bases

HCN

H2CO3

H+ + CN- 1 mol acid produces 1 mol H+, this acid is

monoprotic acid
H+ + HCO3- bicarbonate ion

HCO3H+ + CO32- carbonate ion

1 mol acid produces 2 mols H+, this acid is diprotic acid

Polyprotic acids ionize stepwise.

Problem:
Write the equation for the stepwise ionization of the diprotic acid
H2SO3 (sulphurous acid) .

Brnsted-Lowry theory of acids and bases

Answer:
H2SO3
HSO3-

H+ + HSO3- hydrogen sulfite ion (bisulfite ion)

H+ + SO32- sulfite ion

Strong bases produce OH- ions in high

concentration in solutions.
NaOH Na+ + OHWeak bases have low concentration of OH- ions
in their solutions.
NH3 + H2O
NH4+ + OH8

Brnsted-Lowry theory of acids and bases

stronger acid than H3O+

weaker base than H2O

conjugate pair

HCl + H2O

Cl- + H3O+

conjugate pair
stronger base

weaker acid

than Cl-

than HCl

Brnsted-Lowry theory of acids and bases

weaker acid than H3O+

stronger base than H2O

conjugate pair

CH3COO- + H3O+

CH3COOH + H2O

conjugate pair
weaker base

stronger acid

than CH3COO-

than CH3COOH

CH3COO H .. CH3COO-

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Brnsted-Lowry theory of acids and bases

Conjugate Acid-Base Pairs
strongest

weakest

Acid
HClO4
H2SO4
HCl
HNO3
H3O+
HSO4H3PO4
HF
CH3COOH
H2CO3
H2PO4NH4+
HCO3HPO42H2O

Base
HClO4HSO4ClNO3H2O
SO42H2PO4FCH3COOHCO3HPO42NH3
CO32PO43OH-

weakest

strongest

11

Brnsted-Lowry theory of acids and bases

weaker base than OH-

stronger acid than H2O

conjugate pair

CH3COOH + OH-

CH3COO- + H2O
conjugate pair

stronger base

weaker acid

than CH3COO-

than CH3COOH

weaker base than OH-

stronger acid than H2O

conjugate pair

NH4+ + OH-

NH3 + H2O

conjugate pair
weaker acid

stronger base

than NH4+

than NH3
12

Brnsted-Lowry theory of acids and bases

The strengths of acids are measured by their tendencies to transfer
protons to a base, usually water. For an acid with the general
formula HA,
the equilibrium constant for ionization is obtained by equation:
HA + H2O
H 3 O+ + A K = [H3O+] [A-]
[HA] [H2O]
Water concentration - [H2O], is so large compared to the
concentrations of the ions formed in the equilibrium, that is why
[H2O] is included in another equilibrium constant, the acid ionization
constant, Ka.
Ka = K [H2O] = [H3O+] [A-]
[HA]

The larger the value of Ka, the stronger the acid.

13

Brnsted-Lowry theory of acids and bases

To compare bases we use their tendency to accept protons from
water. For the base with the general formula B, the base
ionization reaction and the related equilibrium constant
expression are:
B + H2O
BH+ + OHK = [BH+] [OH-]
[B] [H2O]

As in the case of the acid ionization constant the [H2O] is included

in the base ionization constant, Kb.
Kb = K [H2O] = [BH+] [OH-]
[B]

The larger the value of Kb, the stronger the base.

Ka and Kb are related in this way:

Ka . Kb = Kw Kw = 1.10 -14
Therefore, if you know one of them, you can calculate the other.
14

Brnsted-Lowry theory of acids and bases

Problem
Lactic acid is a monoprotic organic acid produced in metabolic
reactions. Its Ka is 1.10-4. Calculate the Kb of its conjugate base.
Solution:
Lactic acid HL,
than formation of its conjugate base can be represent with the
equation:
HL + H2O
L- + H3O+
acid

conjugate base

Ka.Kb = Kw
1.10-4.Kb = 1.10-14
Kb =1.10 -14 = 1.10 -10
1.10-4

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Brnsted-Lowry theory of acids and bases

Values of Ka and Kb are very small that is way it is convenient
to define pKa and pKb.
pKa = -logKa
pKb = -logKb
pKa + pKb = pKw = 14
pKa and pKb are used to determine if the acid or base is
strong or weak.
The larger the value of pKa (pKb) , the weaker the acid
(base).
Problem
For CH3COOH/CH3COO pKa + pKb = 14. Calculate the
pKb(CH3COO ) if pKa(CH3COOH) = 4,76. Is the acetate ion
(CH3COO ) a strong base?
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Ionic product of water

Water is amphoteric and can act as an acid and a base with itself.
Water self ionizes at 250C to produce hydronium ions and hydroxide ions.
H3O+ + OHconjugate conjugate
acid
base
One water molecule behaves as an acid, and another behaves as a base in the
reaction.
The equilibrium constant expression is
K = [H3O+].[OH-]
[H2O]2
H2O + H2O
acid base

The concentration of water is so large that it remains virtually constant. It is

included in an alternate equilibrium constant, ion product constant of
water, Kw.
[H2O] = constant Kw = K.[H2O]2 = [H3O+].[OH-]
Kw = [H3O+].[OH-]
Kw ion product constant of water
Kw = 1.10-14 at 25C, it depends on temperature.
In all water solutions Kw = 1.10-14
17

In pure water [H+] = [OH-] = 1.10-7M.

Depending on [H+] solutions are acidic, neutral and basic.
Concentration of H+

pH

Acidic solution

[H+] > 1.10-7M

<7

Neutral solution

[H+] = 1.10-7M

=7

Basic solution

[H+] < 1.10-7M

>7

18

pH value
pH is defined as the negative logarithm of the molarity of
the hydrogen ions (hydronium ions).
pH = log [H+]

for [H+] = 1.10-7M

pH = -log(1.10-7) = - (-7) = 7
This is the pH of neutral solution,
pH of acidic solution is <7
and pH of basic solution is >7
pOH = -log[OH-]

pKw = - logKw

as you know Kw = [H+].[OH-] = 1.10 -14 then

pKw = pH + pOH = 14
19

Problem
Blood sample contains 4,5 . 10-8 M hydronium ions. What is
the pH?
Solution
[H3O+] = 4,5.10-8 M
pH = log [H3O+]
pH = log (4,5.10-8) = -log 4,5 + (-log 10-8)= -0,65 + 8 = 7,35

Problem
A 0,0050 M morphine solution has [OH-] = 8,8.10-5 M. What is
the pH of the solution?
Solution
[OH-] = 8,8.10-4 M
pOH = log [OH-]
pOH = log (8,8.10-4) = -log 8,8 + (-log 10-4)= -0,94 + 4 = 3,06
pH + pOH = 14
pH = 14 pOH = 14 3,06 = 10,94
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acid rain (NOx, SOx)

pH of 4.2 - 4.4

pH

0-14 scale for the chemists

2

acidic
(H+) > (OH-)

normal rain (CO2)

pH = 5.3 5.7

neutral @ 25oC
(H+) = (OH-)
distilled water

10

11

12

basic or alkaline
(H+) < (OH-)

natural waters
pH = 6.5 - 8.5
21

pH
The biological view in the human body
acidic
1

basic/alkaline
7

10

11

22

Methods to measure pH
Using indicators
Hind
H+ + Ind
colour A
colour B
Paper tests like litmus paper and pH paper

23

 Using pH meter
Tests the voltage of the electrolyte
Converts the voltage to pH

24

Buffers
Buffer a solution that prevents a drastic pH change when
either H+ or OH- is added to it.
Each buffer consists of a weak acid and its conjugate base
(salt of that acid)
or weak base and its conjugate acid (salt of that base)
dissolved in water.
Examples:
acetic acid and sodium acetate dissolved in water
CH3COOH / CH3COONa;
ammonia and ammonium chloride dissolved in water
NH3 / NH4Cl

25

Acetate buffer - CH3COOH / CH3COONa

determines pH of the buffer solution

CH3COOH
CH3COONa

CH3COO- + H+
CH3COO- + Na+

CH3COOH / CH3COOThe buffer reacts to neutralize any strong acid or base that is
added to the solution.
could alter pH

HCl
H+ + ClH+ + Cl- + CH3COO- + Na+ CH3COOH + Na+ + ClFor short:

H+ + CH3COO- CH3COOH

26

NaOH Na+ + OH-

could change pH

Na+ + OH- + CH3COOH CH3COO- + Na+ + H2O

Short equation: OH- + CH3COOH CH3COO- + H2O
! In general:
Added acid reacts with the base that present into a solution.
Added base reacts with the acid that present into a solution.

27

Problem
How would the ammonium buffer (NH4OH / NH4Cl) neutralize
the effect of the addition of NaOH and HCl so that the pH value
remains the constant?
Solution:
NH4OH is the base
NH4+ from NH4Cl is its conjugate acid
So, added NaOH must react with the acid
NaOH + NH4Cl
NH4OH + NaCl
For short: OH- + NH4+
NH4OH

HCl added reacts with the base

HCl + NH4OH
NH4Cl + H2O
H+ + OHH-OH
28

Phosphate buffer:
H2PO4- / HPO42How this buffer reacts to neutralize addition of
HCl?
HPO42- + HCl

H2PO4- + Cl-

29

pH of the buffer
What does the pH of buffer depend on? How to calculate
pH of buffer?
First we have to know [H+] in buffer solution. If the buffer
consists of weak acid HA and its salt MA obviously H+ are
produced from HA.
HA
H+ + AKa = [H+][A-]
[H+] = Ka [HA]
[HA]
[A-]
Thus pH=-log[H+]
pH=-logKa + log [A-]
[HA]
pH = pKa + log [A-]
(1)
[HA]
HA - acid
A- - conjugate base
pH depends on the strength of acids and the ratio [A-]
[HA]
30

In the case of buffer consisting of a base and its salt the

equation used for pH calculating is:
pH = 14 pKb + log [B]___
[HB+]

(2)

pH depends on strength of acids or bases

and on the ratio [A-]
[HA]

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The equations ( 1 ) and ( 2 )

are called Henderson Hasselbalchs equations.
pH = pKa + log [A-]
[HA]

(1)

pH = 14 pKb + log [B]___ (2)

[HB+]

They are used to calculate pH of buffers.

32

Buffer capacity is defined as a moles of strong acid or

strong base which must be added into 1 L of buffer solution
in order to change its initial pH with 1 pH unit.
= number of moles of acid (base)
pH
Buffer capacity is higher when solutions are concentrated.

33

Problem
Express the Henderson-Hasselbalchs equation of
carbonate buffer (H2O3/HO3-). Calculate the pH value of
carbonate buffer with [H2O3] = 0,02M and [HO3-] = 0,02M,
pKa = 6,36.
Solution
pH = pKa + log [A-]
[HA]

pKa = 6,36
H2O3 is the acid
HO3- - is its conjugate base, so

pH = pKa + log [HCO3-]

[H2CO3]
pH = 6,36 + log 0,02 = 6,36
0,02
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Buffers in the Body

H2CO3 / HCO3- - bicarbonate buffer; in the blood stream
H2PO4- / HPO42- - phosphate buffer; involved in kidney
functions
protein buffer: plasma protein and hemoglobin
How do these buffers work?
Bicarbonate buffer
1.
HCO3- + H3O+
(aq)

2.

(aq)

H2CO3 + H2O
(aq)

H2CO3

H2O + CO2

(aq)

(aq)

(l )

(g)

H2CO3 + OH-

HCO3- + H2O

(aq)

(aq)

(aq)

(l )

[H2CO3 ] / [HCO3- ] = 1:20

35

Phosphate buffer H2PO4- / HPO42H2PO4- + OHHPO42- + H2O

HPO42- + H3O+

H2PO4- + H2O

[ H2PO4- ]/ [HPO42- ]=1:4

Hemoglobin buffer: HHb / Hb-O2HHb + O2 HbO2- + H+
oxyhemoglobin

HCO3- + H+ H2CO3
H2CO3 CO2 + H2O
Net oxygenation reaction is
HHb + O2 + HCO3- + H+ + H2CO3 HbO2- +H+ + H2CO3 +CO2 + H2O
HHb + O2 + HCO3- HbO2- + CO2 + H2O
36

HHb-NH2 + CO2 HHb-NH-COO- + H+

carbaminohemoglobin

H2O + CO2 H2CO3

H2CO3 HCO3- + H+
Hb-O2- + H+ HHb + O2
The net equation for removal of carbon dioxide is obtained by
summing the three equations.

Hb-O2- + CO2 + H2O HHb + O2 + HCO3deoxygenation reaction

This reaction illustrates the effect of hemoglobin buffer.

37

Acidosis pH of blood lower than 7.28 for a period

of time
Alkalosis - pH of blood higher than 7.40 for a period
of time

38

Brnsted-Lowry theory of acids and bases

Terms

Acid
Base
Amphoteric
Conjugate pair (asid-base pair)
Acid ionization constant Ka
Base ionization constant Kb
Ion product constant of water Kw
pKa, pKb, pKw
pH, pOH, pH of biological fluids
Indicators
Buffers
How to calculate pH of the buffers
Buffer capacity
Buffers in the human body
39