WELCOME TO CHEM 1A

UNIT 2: MATTER-CHANGES
IN INORGANIC SUBSTANCES

Lecture 15
Acid-Base, Buffers
 ORGANIZER

1.ACIDS & BASES?

2. BUFFER SOLUTIONS?
15.1. Acids & Bases

a) Acids, Bases

(i) Definitions-Lewis Acids - accept electrons, eg Mg2+

-Bases -donate electrons, eg NH3

-Arrhenius Acids- liberate H+,

-Bases liberate OH-

-Bronstead/Lowry Acids -donate protons H+

-Bases- accept protons
Consider Bronstead/Lowry acid/base

Bronstead/Lowry Acids –molecules/ions donate protons H+

-Bases- accept protons

Acid particles contain a hydrogen atom bonded polar covalently to

a nonmetal atom eg: HCl, H2O,CH3COOH,NH4+

Bases contain a nonmetal atom with a lone pair of

electrons. eg: OH-, H2O,CH3COO-,NH3 ,CO3 2-
(ii) Conjugate Acid/base Pairs- molecules
and ions that differ in their structure by a
single proton H+. In general:

Acid  conjugate base + proton

When an acid loses a proton it forms its

conjugate base
When a base gains a proton it forms its
conjugate acid

Examples: HCl/Cl-,acid/conjugate base pair

CO3 2-/ HCO3 - base /conjugate acid pair
 (iii) Acidity & Basicity

Acidity Basicity

The acidity of an acid refers to the Basicity refers to the relative

relative number of protons it number of protons accepted per
donates per mole of acid to mole of base on neutralising an
neutralise a base acid

Monoprotic acids can release one Monobasic substances can accept

mole of hydrogen ions per mole of one mole of hydrogen ions per
acid mole of substance
eg HCl H+ + Cl- eg KOH + H+K+ + H2O

Diprotic acids can release two mole Dibasic substances can accept two
of hydrogen ions per mole of acid mole of hydrogen ions per mole of
eg H2SO42H++SO4 2- substance
eg Ca(OH)2 + 2H+Ca2+ + H2O
When hydrogen chloride dissolves in water it
liberates H+ ions which attach themselves to
water:

HCl(g) + H2O(l)  Cl-(aq) + H3O+(aq)

Acid base conjugate conjugate acid
base of HCl of H2O
When carbonate ions dissolve in water they
accept H+ from water:

CO3 2-(aq) + H2O(l) HCO3 - (aq) + OH-(aq)

base acid conjugate conjugate
base
acid of CO3 2- of H2O
 (iv) Amphiprotic Substances- can act as
both an acid and a base
water Hydrogen carbonate Hydrogen sulfate

Acting as an acid water Acting as an acid hydrogen Acting as an acid hydrogen

is proton donor carbonate is a proton donor as it sulfate is a proton donor as it
reacts with water reacts with water
H2O  H+ + OH- HCO3 2-+ H2O H3O+ + CO3- HSO4 - + H2O H3O+ + SO4-

Acting as base water is Acting as a base hydrogen Acting as a base hydrogen

proton acceptor carbonate is a proton acceptor as it sulfate is a proton acceptor
reacts with water as it reacts with water
H 2O + H +  H 3O + HCO3-+ H2O H2CO3 + OH- H2SO3 -+ H2O H2SO4 + OH -

Self Ionisation of water In water, a 0.1molL-1 solution of In water, a 0.1molL-1 solution

yields hydrogen carbonate is in fact of hydrogen sulfate is in fact
alkaline as the second reaction acidic as the first reaction
2H2O ⇌ H3O+ + OH- HCO3- + H2O H2CO3 + OH- is HSO4- + H2O H3O+ + SO4-
Kc=[H3O+][OH-]/[H2O]2 dominant is dominant
kw=kc[H2O]2

Kw=[H3O+][OH-]
 (v) Amphoteric Substances- solids which
dissolve in both acids and bases
Solution Aluminium hydroxide – Zinc oxide-ZnO
Al(OH)3
Acidic Al(OH)3 + 3H+Al3+ + 3 H2O ZnO + 2H+Zn2+ + H2O

Alkaline Acting as a base hydrogen Acting as a base hydrogen

carbonate is a proton acceptor as it sulfate is a proton acceptor
reacts with water as it reacts with water
HCO3-+ H2O H2CO3 + OH- H2SO3 -+ H2O H2SO4 + OH -

Self Ionisation of water In water, a 0.1molL-1 solution of In water, a 0.1molL-1 solution

yields hydrogen carbonate is in fact of hydrogen sulfate is in fact
alkaline as the second reaction acidic as the first reaction
2H2O ⇌ H3O+ + OH- HCO3- + H2O H2CO3 + OH- is HSO4- + H2O H3O+ + SO4-
Kc=[H3O+][OH-]/[H2O]2 dominant is dominant
kw=kc[H2O]2

Kw=[H3O+][OH-]
 (vi) Acid/base Reactions- involves proton
transfer

Examples:

HCl(g) + H2O(l) Cl-(aq) + H3O+(aq)

Acid base conjugate conjugate acid
base of HCl of H2O

HCl(g) + NH3(g)  Cl-(s) + NH4+(s)

Acid base conjugate conjugate acid
base of HCl of NH3
(vii) Acid constant, Ka and pH

Strong acids-100% dissociation, pH= -log[H+]

Example:0.1M HCl 0.1MH+ + 0.1M Cl-

dissoc % =(0.1/0.1 * 100 )=100% and pH =-log(0.1) = 1

Weak acids-partial dissociation, most of acid molecules do not

release their protons

Example:0.1M CH3COOH 0.001MH3O+ + 0.001M CH3COO-

dissoc % =(0.001/0.1 * 100 )=1% and pH is calculated via Ka

route.
For Strong acids there is 100% dissociation and pH= -log[H+]

For Weak acids there is an equilibrium :HA(aq)  H+(aq) + A-(aq) ,

and there is partial dissociation, most of acid molecules do not

release their protons and product concentrations are small,
[H+]=[A-]

Thus Ka =[H+][H+]/[HA] =[H+]2/[HA]

so [H+] = (Ka[HA])1/2 where [HA] = c(HA)

And pH = -log(Ka[HA])1/2 = -log[H+]

Acids dissociation % and pH
solution Measured [H+]=10-pH % dissoc
pH=-log[H+] =[H+]/[acid] *100

0.1 molL-1HCl 1 1 * 10-1 100%

0.1 molL-1 3 1 * 10-3 1%

CH3COOH,

5 1 * 10-5 0.01%
0.1 molL-1 NH4+

Pure H2O 7 1 * 10-7 1.8 * 10-7 %

(viii) Ka, pKa and base strength
As by definition pH= -log[H+] so pKa= -logKa
And as by definition [H+]= 10–pH so Ka= 10–pKa
Acid Formul Ka pKa
a
Strong acid HX Very large, Negative

hydrochloric HCl 1 * 107 -7

Weak acid HA 10-3 to 10-13 3 to 13

Hydrofluoric HF 6.76 *10-4 3.17

Methanoic HCOOH, 1.78 *10-4 3.75
Hypochlorous HClO 3.70 *10-8 7.43
Ammonium NH4+ 5.62 *10-10 9.25
ion
Very, very HA 10-14 or less 14 or more
weak acid
Pure water H2O 1*10-14 14
methanol HCOOH, 1 *10-15 15
As the strength or degree of dissociation of an acid decreases,
then

 Ka value becomes smaller

pKa value becomes larger
 equilibrium [H+] and [A-] decrease
 undissociated equilibrium [HA] increases
Strength of conjugate bases of acids increase

If the acid of the conjugate pair is weak, the conjugate base will be
more likely to accept protons.

If the acid of the conjugate pair is very weak, the conjugate base
will
be strong.
Consider Ka for NH4+(aq) + H20(l) ⇌ NH3(aq) + H30+(aq)

Ka = [NH3][H30+]/ [NH4+]= 5.62 *10-10

The very small size of the ka value indicates

 ammonium ion NH4+(aq) is a very weak acid

 the conjugate base of NH4+(aq) which is ammonia NH3(aq) will

be a “relatively strong” weak base.
(ix)Acid strength and conjugate base
strength
Acid Acid strength Conj.base Conj.base
strength
HCl strong Cl- Very weak

CH3COOH, Weak CH3COO- weak

H2O Very weak OH- strong

C2H5OH Extremely weak C2H5O- Very strong

(x) Ionic Product, Kw, for water

The equilibrium reaction for self ionization of

water is:
2H20(l) ⇌ H30+(aq) + OH-(aq)

Numerically Kc =[H30+][OH-]/[H20 ]2

Then Kc *[H20 ]2=[H30+][OH-]= [H+][OH-]= Kw,

Since Kc & [H20 ]2 are constant then Kw, is also

a
constant
Pure water is neutral. Thus [H+]=[OH-] and
pH=7 so [H+]= [OH-] =10-7 at 25ºc

Since Kw= 10-7 * 10-7= 10-14

So pKw= pH + pOH= 14

(xi) Effects of temperature on Kw

The reaction for self ionization of
water is endothermic:

2H20(l) ⇌ H30+(aq) + OH-(aq) H = +ve

Increasing the temperature favors forward

Increasing the temperature favors forward
reaction resulting in:

 more dissociation
 More hydrogen ions and hydroxide ions
 an increase in Kw

At 100ºC Kw=5.12 *10-13

The increase in kw does not mean that water is

more acidic at higher temperatures. The
concentration of H+ & OH- still remain
identical.
Since[H+] [OH-] =Kw,

then [H+]=(Kw)1/2=(5.12 *10-13 )1/2 = 7.16 *10-7

so pH=-log (7.16 *10-7 ) =6.1

As the water temperature has risen, the pH

scale has been reduced with the central neutral
point now at pH 6.1
(xii) pH & [H+] of Strong Bases

Strong monobasic base MOH releases all OH- when

dissolved in water
 MOH(s)  M+(aq) + OH-(aq)
x mol x mol

 Thus [OH-] =c(base)

For a given pH value or hydrogen ion concentration, Kw

can be used to calculate the hydroxide ion
concentration

Rearranging [H+] [OH-] =Kw, so [OH-] =Kw/[H+]

(xiii) pH & [H+] of Weak Bases

Values for Kb or pKb are rarely given for bases.

Calculations that involve determining the hydrogen ion
concentration and/or the pH of a solution of a weak
base, use the Ka value for the conjugate acid of the
weak base in the expression :
thus [H+]={(Kw * Ka)/ c(base)}1/2

(xiv) Base dissociation constant, Kb

A nonconventional term which refers to the dissociation

of a
Base(usually a weak base) in water.

And pKb= -log Kb

Recall Ka = [NH3][H30+]/ [NH4+]= 5.62 *10-10

Consider Kb for NH3(aq) + H20(l) ⇌ NH4 +(aq) + OH-(aq)

Measured Kb = [NH4][ [OH-]/[NH3]= 1.78 *10-5

so pKb = -log(1.78 *10-5 ) =4.75

Now rearranging Ka & Kb expressions to make [H+]

and [OH-] subject of formula in both equations and
then substitute arranged equations into [H+] [OH-]
=Kw
Eventually Kw= ka * kb

Thus For ammonia & ammonium ion

Kw= ka * kb
Since pKw =14, and log(Ka * Kb) = pKa + pKb

It follows that pKa + pKb =14

Thus for the base/conjugate acid pair NH3/NH4+

NH4+(aq) + H20(l) ⇌ NH3 (aq) + H+(aq) pKa =9.25
NH3(aq) + H20(l) ⇌ NH4 +(aq) + OH-(aq) pKb =4.75

And pKa + pKb = 9.25 + 4.75 =14

Consider a polyprotic acid:

Phosphoric acid, H3PO4, a polyprotic acid, dissociates

stepwise in water releasing one mole of H + at a time.
Each step has a different K a expression and a different Ka
value. The Ka value decreases with each successive step.

The steps for the dissociation of H 3PO4 are: (all are in

aqueous solution)

H3PO4 ⇌ H+ + H2PO41-
H2PO41- ⇌ H+ + HPO42-
HPO42- ⇌ H+ + PO43-

NOTE: the conjugate base for the first step becomes the
Determination of Ka

1.Given a known amount of weak acid in a given volume,

as well as the pH of the resulting solution.

Problem 1 :
A solution of HClO2 is prepared by dissolving 1.369 g of
HClO2 in enough water to make 100.0 mL of solution.
The pH of the resulting solution is 1.36.

Solution:
a. First, write the dissociation equation:

HClO2 ⇌ H+ + ClO2-
b. Next, write the Ka expression:

Ka = [H+] [ClO2-] / [HClO2]

c. Then calculate Ka by setting up a chart as is done with

other equilibrium problems.

The original concentration(OC) for the HClO2 can be

calculated by dividing the mass of the acid by the
volume
in liters and then by the molar mass, which for
HClO2 is 68.46 g/mol
The change for the acid will have a negative sign and the
changes for the H+ and ClO2- will be positive.

The pH is then used to calculate the [H+]

[H+]= inverse log -pH= inverse log(-1.36)= 0.044 M
Since the OC for the H+ was zero, then the change in
concentration for the H+ is +0.0437 M.

This is also the change in concentration for the ClO2-

The change for the HClO2 is a negative 0.0437 M,
so the equilibrium concentration(EC) would be 0.2000 M -
0.0437 M = 0.01563 M.

An equilibrium chart tracts the changes in concentration

 Equilibrium.chart
species Original Change in Equilibrium
conc conc. conc.

HClO2
 Ka = [H +][ClO2-] / [HClO2] = [0.0437][0.0437] / [0.1563] = 0.0122
0.2000 -0.0437 0.1563
Ka = [H+][ClO2-] / [HClO2] = 0.0122
[H+]
0 +0.0437 0.0437

ClO2-
0 +0.0437 0.0437
2.Given the original concentration and percentage
dissociation of the acid.

Problem 2:

A 0.300 M phosphorous acid solution is 33.3% dissociated in the

first-step.

The equation for the first-step dissociation is

H3PO3 <____> H+ + H2PO3-

The Ka expression is: Ka = [H+] [H2PO3-] / [H3PO3]

33.3% dissociation - 33.3% of the phosphorous acid has

dissociated or changed into H+ and H2PO3-.
The change in the H3PO3 is therefore, (0.300)(0.333) =
0.0999 M.

It has a negative sign, and the change for the two ions is
a positive 0.100 M each.

The remainder of the problem is carried out as any other

equilibrium problem.
 Equilibrium. Chart-Results
original conc. equilibrium conc
species change
(M) (M)

H3PO3 0.300 -0.0999 0.200

H+ 0 +0.0999 0.0999

H2PO3- 0 +0.0999 0.0999

Ka = [H+] [H2PO3-] / [H3PO3] = 0.0499

3.Determination of the [H+] or pH of a solution of a weak acid
when the original concentration is known.

Problem 3 :

Phenol (C6H5OH) has a Ka = 1.6 x 10-10. Determine the [H+] in a

solution prepared by dissolving 0.500 mol of phenol to form 5.00 L of
solution.

Solution
We don't know any of the EC values, so we let the change
for each be "x".

The phenol change would be -x, giving the EC for phenol as

0.100 - x.

The change for the two ions would be +x for each, with an
 Equilibrium. Chart-Results
original conc. equilibrium conc
species change
(M) (M)

C6H5OH 0.100 -x 0.100-x

H+ 0 +x x

C6H5O- 0 +x x

Ka = [H+] [C6H5O-] / [C6H5OH] = [x] [x] / [0.100-x] = 1.6 x 10-10

 Assumption!!
Most weak acids have such small dissociation constants

we may assume the amount dissociated is so much

smaller than the original concentration(OC) it is
negligible when compared to the original concentration

A good rule to follow is when the size of Ka is greater than

or equal to 10-5 then x cannot be ignored in the
denominator but if it is smaller than 10-5 it can probably
be ignored.

The mathematics are certainly simplified when x is

ignored.
15.2. Buffer Solutions

Buffer solutions – maintain constant pH upon addition of

small amounts of acid(H+) or alkali (OH-)

Buffer solutions-are essential for

 maintaining a constant internal environment in living

organism
 Medical/industrial processes which are pH sensitive
Buffer solutions contain equal amounts of
 A weak acid & its conjugate base

Example: ethanoic /acetate ion

bicarbonate/carbonate ion

Aweak base and its conjugate acid

Example: ammonia/ammonium ion or
methylamine/methylamine ion
Buffer solutions maintain a constant pH because
 The added OH- are protonated to give water
 The added H+ protonate the base or conjugate

base

Example: 1.Ethanoic acid/ ethanoate ion buffer –

addition of base to acid

CH3 COOH(aq) + OH-(aq) → CH3COO-(aq) +

H2O(l)

Example: 2 addition of acid to conjugate base

- +
Buffer Zone: the range of effective pH control is
one pH unit below and above pka.ie (pka±1)

Example: 1.Ethanoic acid/ ethanoate ion buffer

pka=4.76 and buffer zone is pH 3.76-5.76

Example: 2 ammonia/ammonium chloride

pka=9.25 and buffer zone is pH 8.25-10.25
Buffer solutions calculations are limited to
monoprotic acids

Example: 1. For general dissociation of weak

acid HA to its conjugate base A-

HA(aq)+H2O(l)⇋H3O+(aq) +A-(aq)

The reaction above generalizes to weak acids, conjugate

acids
weak acid + H2O(l)⇋H3O+(aq) + conjugate base
conjugate acid + H2O(l)⇋H3O+(aq) + base
The reaction above generalizes to any buffer
acidic species+ H2O(l)⇋H3O+(aq) + base species

For [H+]=[H3O+], ka=[H+][basic species]/[acidic species]

Thus[H+]=ka[acidic species]/[basic species]

And -log[H+]= -log{ka[acidic species]/[basic species]}

Yields pH=pka-log{[acidic species]/[basic species]}

or

pH=pka+ log{[basic species]/[acidic species]}

when [basic species]=[acidic species] Then ka=[H+] and
pH=pka

Thus for buffer solutions equimolar for acidic and basic

species ka=[H+] and pH=pka

Example : Calculate the pH of a buffer solution when

0.05mol of sodium methanoate HCOONa is added to
1litre of a solution containing 0.15mol of methanoic acid,
HCOOH pka=3.75
Solution:
pH=pka+ log{[basic species]/[acidic species]}
=3.75+ log{0.05/0.15}
=4.23
pH of buffer solutions affected by dilution

Example : Calculate the pH of a buffer solution when 80 mLsof 0.10M of

sodium butanoate CH3(CH2)2COONa is added to 20mLs of 0.10M of butanoic
acid, CH3(CH2)2COOH , ka=1.74 *10-5 ,pka=4.76

Solution:

First calculated concentrations in final solution

[CH3(CH2)2COO-] =(original conc x original vol)/(final vol)

=(0.10 x 80)/(20 + 80)
= 0.08M

[CH3(CH2)2COOH] ==(original conc x original vol)/(final vol)

=(0.10 x 20)/(20 + 80)
= 0.02M

Now using pH =pka+ log{[basic species]/[acidic species]}

=4.76+ log{0.08/0.02}
Preparation of buffer solutions

Buffer solutions are prepared by making solutions that

contain approximately equal molar concentrations of a
weak acid and its conjugate base, or a weak base and its
conjugate acid.

Example 1 : Prepare weak acid/conjugate base buffer-

ethanoic acid/sodium ethanoate of pH=4.76 since
ethanoic acid pka=4.76
Preparation of buffer solutions

Method 1

Neutralise a known amount of ethanoic acid(xmol ) with

sodium hydroxide. This gives x mol of ethanoate ions

NaOH + xCH3COOH → xCH3COO- + H2O

Add another xmol ethanoic

xCH3COONa + xCH3COOH = equimolar buffer, pH=4.76

Method 2:
Add an amount of sodium ethanoate solid(xmol)
to a solution that contains the same amount of
ethanoic acid.

Amount of ethanoic acid calculated from n=Cv,

Cv=x

xCH3COONa + xCH3COOH = equimolar buffer,

pH=4.76
Method 3:
Use half the stoichiometric amount of sodium hydroxide
(xmol) required to react with twice the amount (2xmol) of
ethanoic acid.
xNaOH + 2xCH3COOH = xCH3COONa + H2O+ xCH3COOH

Half the acid(xmol) is converted to ethanoate ions and the

other half of the acid(xmol) remains:

xCH3COONa + xCH3COOH = equimolar buffer, pH=4.76

 THANK YOU FOR
LISTENING

Do tutorial 2.8 questions in study guide

 EXPERIMENT 8a

Experiment 8- Solutions & Concentrations