CLASSICAL METHODS

Instructor: Professor Aderemi O. Ogunfowokan

Mobile phone: 0803 438 7270; email: aogunfow@oauife.edu.ng
Office: Chemistry Department, First floor, White house
CHM 208 Lecture on Chemical Methods- 1

Titrimetric
Measurement
Chemical method
Gravimetric
Measurement

In the early years of Chemistry, most analyses were carried out by separating the components

of interest (the analytes) in a sample by precipitation, extraction, or distillation. For

qualitative analyses, components of samples were separated and then treated with reagents

which yielded products that were recognized by their boiling point, melting point, odours,

colours, solubilities in different solvents, their refractive indexes or optical activities.

Quantitative analyses: (amount of analytes in a sample) were determined by Gravimetric or

Titrimetric measurements: this is the measurement of the volume or weight of a standard

reagent required to react completely with the analyte in a given sample.

Gravimetric Measurement: the mass of the analyte or some compounds produced from the

analytes are measured.

A. PRINCIPLE OF TITRIMENTRY TECHNIQUE

- Involves the addition of a standard solution of known concentration to solution of the

analyte in order that the stoichiometry of the equivalence point of the reaction may be

located.

- The amount of the analyte is then calculated from the known concentration of the

standard reagent consumed in the reaction.

- Hence titrimetric analysis involves the reaction between analyte and the reagent to

stoichiometric end point.

- End point detection is by physicochemical or electrochemical methods or visual

indicator.

- The word stoichiometry above implies that the reaction must be followed by balanced

reactions.

Some definitions in titrimetric analyses

- Titrant: is defined as the standard solution/reagent used in a titration. It is a solution

of known concentration.

- Titrand: is the solution to which the titrant is added. It usually contains the analyte

of interest

- End point: this is the pt. in the progress of reaction between reagent and the analyte

which may be precisely located and can be related to the equivalence point of the

reaction. It is the point in a titration where an indicator changes colour.

- Equivalence Point: is the pt. at which the reaction between analyte and reagent is just

complete

- Titration curve: This is a record of some function of concentration of some titrant

species e.g pH is a function of the reactant added.

- Indicator: Is an organic acid which has a range at which pH change occur. It is a

reagent or device used to indicate when the end point has been obtained

Classification of Titrimetric Analysis

(a) Acid base titrant- e.g NaOH vs HCl

(b) Precipitation titration- In precipitation titration, the titrant forms an insoluble product

with the analyte e.g determination of Chloride ion using silver nitrate
(c) Redox titration- this involves the titration of an oxidizing agent with a reducing agent

and vice versa e.g KMnO4 vs Fe2+ etc

(d) Complexometric titration- in this case the titrant is a reagent that forms a water

soluble complex with the analyte, a metal ion. The titrant is often the chelating agent

e.g. ethylene diamine tetraacetic acid (EDTA)

Acid Base Titration

- For any titrimetric analysis at all we must talk on the primary (1o) standards because

accuracy depends on the 1ostandard.

- A primary standard is defined as the reagent used in the estimation of the

concentration of a secondary standard. It is a reagent of stable concentration. It is

otherwise called American Chemical Society (ACS) reagent-grade. They are

generally at least 99.95% pure.

- Examples of Primary Standards are-

 Potassium Hydrogen Phthalate- KHC8H4O4

 Sulfamic Acid- HSO3NH2

 Potassium Hydrogen Iodate- KH(IO3)2

 Sodium Carbonate- Na2CO3

 Tris(hydroxymethyl)aminomethane (THAM), (CH2OH)3CNH2

 Potassium Oxalate- K2C2O4

Desirable Properties of a primary Standard

(i) It must be in highest purity, the total amount of impurity must not be than 0.01 to

0.02%

(ii) Stability: it must be stable in such a way that it can be stored for a long time

without decomposition. It must not absorb O2 or air i.e. it must not be

hygroscopic. Also it must not lose weight on exposure to air.

(iii) Availability: it must be readily or easily available with a reasonable cost.

(iv) High equivalent weight: It must have a reasonably high equivalent weight to

avoid loss and to reduce weighing errors.

(v) Absence of hydrate of water : In this case deliquescent or hygroscopic substances

will not be suitable e.g NaCl, H2SO4 are not suitable primary standards.

- Note that a secondary (2o) standard is a solution that do not give a stable

concentration

QUALITIES OF AN IDEAL STANDARD SOLUTION

(1) Its concentration should remain constant for some time to eliminate need for

neutralization.

(2) It reaction with the analyte should be rapid

(3) There should be complete reaction with between the analyte and the standard

solution.

(4) Reaction between reagent and the analyte should be stoichiometric.

(5) There must be a method for detecting end point.

End Point Detection

- This is based on the abrupt change in pH at the vicinity of the end point.

- End point detection is a prerequisite for precise and accurate titration

- It can be located either by monitoring the properties of the titrand or by monitoring

the condition of the solution when a slight excess of the titrant is added after the end

point is reached.
 Acid Base Titration

- This sis same as neutralization titration in which we have:

𝐻 + + 𝑂𝐻 → 𝐻2 𝑂

- Note that the range in pH change of reaction depends on the concentration of the acid

and indicator.

Consider the reaction between 𝑯+ and 𝑶𝑯 - to give 𝑯𝟐 𝑶

2𝐻2 𝑂 ⇌ 𝐻3 𝑂+ + 𝑂𝐻 − or H2O ⇌ H+ + OH-

[𝐻 + ][𝑂𝐻 − ]
𝐾𝑒𝑞𝑖𝑙 =
𝐻2 𝑂

𝐾𝑤 = [𝐻 + ][𝑂𝐻 − ] − − − −(2)

𝑊ℎ𝑒𝑟𝑒: 𝐾𝑤 = 𝑖𝑜𝑛 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑐𝑜𝑛𝑠𝑎𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 = 1.0 𝑥 10−14

By definition:

𝑝𝐻 = − log[𝐻 + ]

𝐼𝑛𝑡𝑟𝑜𝑑𝑢𝑐𝑒 − log 𝑖𝑛 𝑒𝑞𝑛 2.

− log 𝐾𝑤 = − log[𝐻 + ] + − log[𝑂𝐻 − ]

Therefore p𝐾𝑤 = 𝑝𝐻 + 𝑝𝑂𝐻

𝑝𝐾𝑤 = −𝑙𝑜𝑔𝐾𝑤 = −𝑙𝑜𝑔1.0 𝑥 10−14 = 14 = 𝑝𝐻 + 𝑝𝑂𝐻

𝑖. 𝑒. − log 𝐾𝑤 = 𝑝𝐾𝑤 = 14

INDICATOR FOR ACID BASE TITRATION

Theory of Indicator behaviour

Acid base indicators are fairly high molecular weight weak organic acids or bases, which

upon dissociation or association undergo structural changes that give rise to alterations in

color. The indicator is usually added to the solution and visually detect as a color change.

The color of the ionized form of the indicator is usually different from the non-ionized

form. One form may be colorless, but the other form may be colored.
 SYMBOLIC REPRESENTATION OF TYPICAL REACTION OF ACID BASE

INDICATOR

Suppose we have an indicator of a weak acid, designated Hln, and assume that the non-

ionized form is red while the ionized form is blue thus:

(a) H2O + Hln ⇌ H3O+ + ln-

Acid color (red) Basic color (blue)

(b) ln- + H2O ⇌ lnH+ + OH-

Basic color acid color

( Base indicator)

At equilibrium concentrations for each reaction can be calculated thus:

[𝐻3 𝑂 + ][ ln− ]
𝑘𝑎= [𝐻ln]
-------------- (3)

[ln𝐻 + ][𝑂𝐻 − ]
𝑘𝑏= [ln]
----------- (4)

Rearranging equations 3 & 4

[ ln− ] 𝑘𝑎
[𝐻𝑙𝑛]
= [𝐻3 𝑂 + ]
------ (5)

[ ln𝐻 + ] 𝑘𝑏
[ 𝑙𝑛]
= [𝑂𝐻 − ]
-------------------- (6)

But 𝑘𝑤 = [𝑂𝐻 − ][𝐻3 𝑂+ ]

𝑘𝑤
[𝑂𝐻 − ] = [𝐻 +]
substitute this is equation 6
3𝑂

[ ln𝐻 + ] 𝑘𝑏 𝑘𝑏 [𝐻3 𝑂+ ]
= =
[ 𝑙𝑛] 𝑘𝑤 𝑘𝑤
[𝐻3 𝑂+ ]

𝐵𝑢𝑡 𝑘𝑏 and 𝑘𝑤 𝑎𝑟𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

[ ln𝐻 + ]
Hence [ 𝑙𝑛]
= [𝐻3 𝑂+ ]

[ ln𝐻 + ]
Hence as [𝐻3 𝑂+ ] change there will be a change in concentration of ratio [ 𝑙𝑛]
Again recall that 𝑘𝑤 = [𝑂𝐻 − ][𝐻3 𝑂+ ]

Therefore [𝐻3 𝑂+ ] = 𝑘𝑤 /[𝑂𝐻 − ]

Substitute this in equation 5 and solve as before you will get:

[ ln− ]
[𝐻𝑙𝑛]
= [OH-]

[ ln− ]
Hence a change in [OH-] will result in change of ratio [𝐻𝑙𝑛]

With indicator in which both forms are colored, generally only one color is observed

if the ratio of the concentration of the two forms is 10:1; only the color of the more

concentrated form is seen. When only the color of the non-ionized form is seen, then

[ ln− ]
= 1/10
[𝐻𝑙𝑛]

[ ln− ] 1
Hence for [𝐻𝑙𝑛]
≤ 10 acid color predominate

[ ln− ] 10
For [𝐻1𝑛 ]
≤ Base color predominate
1

To evaluate of the range of [𝐻 + ] concentration needed to effect the color change of

indicator we have:

[𝐻3 𝑂 + ][ ln− ]
from equation 3----- 𝑘𝑎= [𝐻ln]

1
𝑘𝑎 = [𝐻3 𝑂+ ]
10

[𝐻3 𝑂+ ] = 10𝑘𝑎 -- (7)

𝑓𝑜𝑟 𝑓𝑢𝑙𝑙 𝑏𝑎𝑠𝑖𝑐 𝑐𝑜𝑙𝑜𝑟 𝑓𝑟𝑜𝑚 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 , 𝑖𝑓:

[𝐻3 𝑂+ ][ ln− ]
𝑘𝑎=
[𝐻ln]

𝑘𝑎 = [𝐻3 𝑂+ ]10
𝑘𝑎
Therefore [𝐻3 𝑂+ ] = --- (8)
10
Indicator range is given from equations 7 and 8 by taking the negative log of the 2 equations:

𝑘
- log [𝐻3 𝑂+ ] = − log 10𝑘𝑎 𝑡𝑜 − log 10𝑎

- log [𝐻3 𝑂+ ] = 𝑝𝐻 = − log 10 − log 𝑘𝑎 𝑡𝑜 − 𝑙𝑜𝑔10−1 − log 𝑘𝑎

= −1 + 𝑝𝑘𝑎 𝑡𝑜 (+1) −log 𝑘𝑎

𝑝𝐻 = −1 + 𝑝𝑘𝑎 𝑡𝑜 + 1 + 𝑝𝑘𝑎

Therefore 𝑝𝐻 𝑟𝑎𝑛𝑔𝑒 = 𝑝𝑘𝑎 ± 1

e.g. 𝑖𝑓 𝑝𝐻 = 5, 𝑝𝐻 𝑟𝑎𝑛𝑔𝑒 = 4 𝑡𝑜 6 𝑖. 𝑒 4 − 6

So the pH in going from one color to the other has changed from pKa – 1 to pKa + 1. This is a

pH change of 2, and most indicators require a transition range of about two pH units. During

this transition the observed color is a mixture of the two colors. Midway in the transition, the

concentrations of the two forms are equal, and pH = pKa . Obviously, then the pKa of the

indicator should be close to the pH of the equivalence point.

There are 3 major types of acid base titrations

(i) Strong acid vs strong base

(ii) Strong acid vs weak base

(iii) Weak acid vs. strong base

Choice of an Indicator for an acid-base titration

An indicator for an acid base titration must fulfil two main conditions:

 It must undergo a readily detectable color change for the addition of a very small

quantity of titrant

 The color change must occur at (or very close to) the equivalence point.

The Table below shows the list of indicators suitable for different types of acid-base

titrations.
Type of Titration Suitable Indicator

Strong acid-strong base Any indicator-methyl orange, bromothymol

blue, phenolphthalein etc

Weak acid-strong base Phenolphthalein

Strong acid-weak base Methyl orange, bromothymol blue

Weak acid-weak base None (titration curve has no vertical section

at equivalence point so the first condition

above is not satisfied)

TITRATION CURVES

Titration curve for acid-base reactions is a plot of pH (or pOH) against milliliters of titrant.

It is a plot showing the change in pH of the solution in the conical flask as the reagent is

added from the burette.

(a) Strong acid Vs. strong base

Note that bcause it is a strong acid-base reaction, ionization is complete and the reaction can

be simplified as: H+ (aq) + OH- (aq) H2O (l)

100ml of 0.1MHCl Vs 100ml of 0.1M NaOH

Note that in this case ionization is complete:

Assume initially: 𝑝𝐻 = − log 10−1 = 1

𝐴𝑡 90% 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐻𝐶𝑙 𝑙𝑒𝑓𝑡 = 10%

10
⇒ 𝑝𝐻 = −𝑙𝑜𝑔 𝑥 0. 1 = −𝑙𝑜𝑔10−2 = 2
100

𝑎𝑡 99% 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐻𝐶𝑙 𝑙𝑒𝑓𝑡 = 1%

 1 𝑥 0.1
⇒ 𝑝𝐻 = − 𝑙𝑜𝑔 = −𝑙𝑜𝑔10−3 = 3
100

𝑎𝑡 99.9% 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝐻𝐶𝑙 left = 0.1%

0.1 𝑥 0.1
⇒ 𝑝𝐻 = −𝑙𝑜𝑔 = −𝑙𝑜𝑔10−4 = 4
100

𝑝𝐻 𝑟𝑎𝑛𝑔𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑛𝑑 𝑝𝑡 𝑜𝑓 𝑡ℎ𝑒 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑖𝑠 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 99.9 − 100.1𝑚𝑙

𝑖𝑓 100.1𝑚𝑙 𝑜𝑓 𝐻𝑎𝑂𝐻 𝑖𝑠 𝑢𝑠𝑒𝑑 ⇒ 0.1𝑚𝑙 of NaOH was in excess

0.1 0. 1
⇒ 𝑝𝑂𝐻 = −𝑙𝑜𝑔 𝑥 = 4
100 1

Recall that pH + pOH = 14

Therefore 𝑝𝐻 = 14 − 4 = 10

Summary:

𝐻𝑒𝑛𝑐𝑒 𝑝𝐻 = 1 𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 0𝑚𝑙

𝑝𝐻 = 2 90 𝑚𝑙

pH = 3 99 ml

𝑝𝐻 = 4 99.9 𝑚𝑙

Below is an example of titration curve of a strong base added to a strong acid of same

molarity (e.g. using mL 0.1M NaOH added to 50mL 0.1M HCl)

 mL 0.1M NaOH added

*Note that the pH range is (4-10) (the vertical portion of the curve) which is so large that

all the indicators can usually be used to follow the titration (Any indicator will do)

Titration curve for a Weak acid vs. strong base e.g. Acetic acid vs Sodium hydroxide

0,1M 100ml Acetic acid vs 0.1M 100ml NaOH

HOAC + NaOH = NaOAC + H2O

Note that acetic acid (HOAC or CH3COOH) is a weak acid hence ionization is

incomplete.

- The initial pH cannot be 1

1. Hence consider the Kac HOAC = H+ + OAC-

[𝐻 + ][𝑂𝐴𝐶 − ]
𝐾𝐴𝐶 = [ 𝐻𝑂𝐴𝐶]
= 1.75 𝑥 10−5 (𝐾𝑎 𝑓𝑜𝑟 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑)

𝑙𝑒𝑡 [𝐻 + ] 𝑎𝑛𝑑 [𝑂𝐴𝐶 − ] 𝑏𝑒 𝑡𝑎𝑘𝑒𝑛 𝑡𝑜 𝑏𝑒 𝑥 𝑟𝑒𝑠𝑝𝑒𝑐𝑡𝑖𝑣𝑒𝑙𝑦 ⇒ [𝐻𝑂𝐴𝐶]) = 𝑐 − 𝑥 at

equilibrium

But x <<< c

𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒 𝑐 − 𝑥 = 𝑐

𝑥2
𝐾𝐴𝐶 =
𝑐

Given that KAC for acetic acid = 1.75 x 10-5 then we have:

𝑥2
1.75 𝑥 10−5 =
0.1

𝑥 = √1.75 𝑥10−6 = 0.00132

𝑝𝐻 = − log 0.00132

pH = 2.878 = 2.88 𝑎𝑡 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑠𝑡𝑎𝑔𝑒

2. 𝐵𝑢𝑡 𝑎𝑡 𝑚𝑖𝑑 𝑝𝑜𝑖𝑛𝑡 50/50

[𝑂𝐴𝐶 − ] = [𝐻𝑂𝐴𝐶]
 [𝑎𝑐𝑖𝑑]
⇒ 𝑝𝐻 = 𝑝𝐾𝑎 − 𝑙𝑜𝑔
[𝑠𝑎𝑙𝑡]

[50]
𝑝𝐻 = 𝑝𝐾𝑎 − 𝑙𝑜𝑔 [50]

𝐵𝑢𝑡 𝑝𝐾𝑎 = −𝑙𝑜𝑔𝐾𝑎 = − log 1.75 𝑥 10−5

𝑝𝐻 = −𝑙𝑜𝑔1.75 𝑥 105 − log 1

𝑝𝐻 = 4.757 𝑎𝑡 𝑡ℎ𝑒 𝑚𝑖𝑑 𝑝𝑡

3. The point of abrupt change in pH starts from where we add 0.1ml of free HOAC to

0.1m of free NaOH.

If 99.9 ml of NaOH was added we have 0.1ml free HOAC

⇒ 99.9 𝑚𝑙 𝑜𝑓 𝐻𝑂𝐴𝐶 𝑚𝑢𝑠𝑡 ℎ𝑎𝑣𝑒 𝑏𝑒𝑒𝑛 𝑎𝑑𝑑𝑒𝑑.

0.1
⇒ 𝑝𝐻 = −𝑙𝑜𝑔𝐾𝑎 − log
99.9

⇒ 𝑝𝐻 = 𝑝𝐾𝑎 + 3

𝑝𝐻 = 7.77 ≈ 8: ⇒ 𝑡ℎ𝑒 𝑝𝑜𝑖𝑛𝑡 𝑎𝑡 𝑤ℎ𝑖𝑐ℎ 𝑡ℎ𝑒 𝑎𝑏𝑟𝑢𝑝𝑡 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑝𝐻 𝑠𝑡𝑎𝑟𝑡𝑠.

4. 𝑆𝑢𝑝𝑝𝑜𝑠𝑒 𝑤𝑒 ℎ𝑎𝑣𝑒 0.1𝑚𝑙 𝑓𝑟𝑒𝑒 𝑁𝑎𝑂𝐻 ⇒ 𝑤𝑒 ℎ𝑎𝑣𝑒 0.1% 𝑁𝑎𝑂𝐻 𝑙𝑒𝑓𝑡

0.1 0.1
⇒ 𝑝𝑂𝐻 = − log 𝑥 =4
100 1

𝑝𝑂𝐻 = 4, 𝑝𝐻 = 14 − 4 = 10

pH range is 8-10 hence limited number of indicator can be used to follow the titration.

Below Is the Titration curve of a weak acid vs strong base:

 Volume (mL) of 0.1M NaOH to the acid

*Note from the curve that the pH range is narrow (8-10) {vertical section in the curve}

hence limited number of indicators can be used to follow the titration. Likely indicator =

phenolphthalein.

Strong acid Vs. weak base e.g. HCl Vs. NH4OH

𝑝𝐾(𝑁𝐻4 𝑂𝐻)=1.85 𝑥 10−5

[𝑂𝐻] = √𝐾𝑏𝑎𝑠𝑒 𝐶𝑏𝑎𝑠𝑒

1/2
[𝑂𝐻] = (𝐾𝑏𝑎𝑠𝑒 𝐶𝑏𝑎𝑠𝑒 )
1
Taking -log of both sides: - log [OH] = 2 (−𝑙𝑜𝑔𝑘𝑏𝑎𝑠𝑒 + {− log 𝐶𝑏𝑎𝑠𝑒 })

1 1
- log [OH] = 2 𝑝𝑘𝑏 − log 𝐶𝑏𝑎𝑠𝑒
2

1 1
pOH = 2 𝑝𝑘𝑏𝑎𝑠𝑒 − 𝑙𝑜𝑔𝐶𝑏𝑎𝑠𝑒
2

1 1
= (2 𝑥 1.85 𝑥 10−5 )− 2 log 0.1

1
= 9.25𝑥 10−6 +
2

𝑝𝐻 = 14 − 𝑝𝑂𝐻
The abrupt pH range at transition state is 6.74-4.0 which falls in the acid region.

Because the pH transition range is narrow, hence choice of indicator is restricted.

- Another disadvantage of this is that the end point cannot be sharp/satisfactory, hence

we can have titration error.

- This is the case which Kjeldahl analysis method of N2 determination. In which case

instead of titrating weak base NH4SO4with strong acid, we dissolve in strong acid and

back titrate with strong base.

The indicators that can follow this reaction are: methyl orange & methyl red.

Below is the titration curve for titration involving strong acid vs weak base:

mL of 0.1M of NH4OH

*Note from the curve that the pH range is narrow (4.0 to 6.7.4) {vertical section in the

curve} hence limited number of indicators can be used to follow the titration.

Weak Acid vs weak base e.g. CH3COOH vs NH4OH

In this case the pH change in the region of the equivalence-point is very much less

than sharp than in the previous examples and there is no vertical section in the curve.

Therefore the equivalence point depends on the relative strengths of the weak base
and the weak acid being used which both have Ka =Kb giving an equivalence point of

pH = 7. Hence it is difficult to monitor the end point {since there is no vertical

section in the curve}and therefore no indicator can be used to detect the end point.

Titration curve for weak acid vs weak base

Table: pH range color change for some Indicators in Acid base Titration

Indicator type pH range of color Acidic color Alkaline color

change

Methyl Red 4.2-6.3 Red Yellow

Phenolphthalein 8.3-10.0 Colorless Red/Pink

Methyl orange 3.1-4.4 Red Yellow

Congo red 3.0-5.0 Violet Orange

 Litmus 4.1-8.3 Red Blue

Alizarin yellow 10-12 Yellow Red

Titration of Na2CO3- A Diprotic Base

Na2CO3 is a Bronsted base because it has the ability to accept proton. It is usually

used as 1o standard in titration of strong acid. Hydrolysis of Na2CO3 in water is in 2

stages thus:

𝐶𝑂32− + 𝐻2 𝑂 ⇌ +𝐻𝐶𝑂3− + 𝑂𝐻 −

𝑘𝑤
𝐾𝐻1 = 𝐾𝑏1 = = 2.1 𝑥 10−1
𝐾𝑎2

2nd stage of hydrolysis

𝐻𝐶𝑂3− + 𝐻2 𝑂 ⇌ 𝐶𝑂2 + 𝐻2 𝑂 + 𝑂𝐻 −

𝑘𝑤
𝐾𝐻2 = 𝐾𝑏1 = = 2.3 𝑥 10−8
𝐾𝑎1

𝐾𝑎1 𝑎𝑛𝑑 𝐾𝑎2 𝑟𝑒𝑓𝑒𝑟 𝑡𝑜 𝐾𝑎 𝑣𝑎𝑙𝑢𝑒𝑠 𝑜𝑓

H2CO3 and Kb values are calculated values for salt of weak acids and bases

𝑎𝑡 𝑝𝐻 = 4.0;

𝐾𝑎1 &𝐾𝑎2 𝑟𝑒𝑓𝑒𝑟 𝑡𝑜 𝐻2 𝐶𝑂3

𝐻𝐶𝑂3− 𝑖𝑠 𝑡ℎ𝑒 𝑐𝑜𝑛𝑗𝑢𝑔𝑎𝑡𝑒 𝑎𝑐𝑖𝑑 𝑓𝑜𝑟 𝐶𝑂32−

𝐻2 𝐶𝑂3 𝑖𝑠 𝑡ℎ𝑒 𝑐𝑜𝑛𝑗𝑢𝑔𝑎𝑡𝑒 𝑎𝑐𝑖𝑑 𝑓𝑜𝑟 𝐻𝐶𝑂3−

To obtain a good separation of the two end points Kb value should differ by at least 104
Titration curve for Na2CO3 versus HCl is shown as a solid line in the figure above

- For the 1st titration a sharp end point cannot be obtained because of the formation of

CO2 beyond the end pt.

- For the 2nd titration, the 2nd end point can also not be sharp because of:

- the gradual change in pH and Kb value which is < 10-6

- the 𝐻𝐶𝑂3− /𝐶𝑂2 buffer system interferences

REMEDY

- The sharp end point can be improved upon by boiling off CO2

- Hence removing the buffer system by reverting the color of the indicator to yellow

- Cool the solution, and then titrate to a color change. The use of phenolphthalein

indicator at the first titration is just to determine the approximate value of where the

second end point will be using methyl arrange.

BUFFER SOLUTION
 - Is a solution that resists change in pH when a small amount of acid or base is added or

when the solution is diluted.

- Buffer solution usually consist of a weak acid and its salt or a weak base and its salt

common examples are:-

(i) Acetic acid and sodium acetate

(ii) Ammonia solution NH4OH and ammonium chloride NH4Cl.

(iii) NaH2PO4 and Na2HPO4.

- If we consider titration curves we find out that generally 2 regions can be

recognized:-

(a) Region of abrupt pH change and the curve is vertical ie big change in pH with little

addition of acid or base.

(b) The region where the curve is flat which is the horizontal region – there is very little

change in the pH in this region with addition of acid or alkaline; such solution within

this region are said to have buffer action. They are referred to as buffer solution

Consider the equation

𝐻𝐴 + 𝐻2 𝑂 ⇌ 𝐻3 𝑂+ + 𝐴− --- (1) –conjugate acid base pair

𝐴− + 𝐻2 𝑂 ⇄ 𝐻𝐴 + 𝑂𝐻 − --- (2)

[𝐻3 𝑂+ ][𝐴− ]
𝐾𝑎 = 𝑓𝑟𝑜𝑚 𝑒𝑞𝑛 (1)
[𝐻𝐴]

[𝐻𝐴][𝑂𝐻 − ]
𝐾𝑏 = 𝑓𝑟𝑜𝑚 𝑒𝑞𝑛 (2)
[𝐴− ]

Where [𝑂𝐻 − ] and [𝐻3 𝑂+ ] depends both on 𝐾𝑎 , 𝐾𝑏, and ratio [𝐻𝐴]⁄[𝐴− ]

- From the treatment of the above equation:

𝐾𝑎 [𝐻𝐴]
[𝐻3 𝑂+ ] = ** lot of assumptions are made to arrive at this equation
[𝐴− ]

[𝐻𝐴] = ℱ𝐻𝐴 (Formation concentration for acetic acid)

[𝐴− ] − ℱ𝑁𝑎𝐴 (Formation concentration for sodium salt eg. sodium acetate)
 Introducing –log to equation **:

log[𝐻3 𝑂+ ] = − log 𝐾𝑎 + log [𝐴− ]⁄[𝐻𝐴]

Hence the HENDERSON HASSELBALCH EQUATION

[𝐴− ]
i.e pH = 𝑝𝐾𝑎 + log [𝐻𝐴]

The equation states that [𝐻 + ] of a solution of a weak acid or its conjugate base

(Buffer solution) is independent of dilution but dependent only on the ratio of the 2

solutes.

BUFFERING CAPACITY

- Show the amount of Acid or Base that must be added to such buffer without a large

change in pH.

- It is the number of equivalents of strong acid or base needed to cause 1.00L of the

buffer to undergo a 1.00 unit change in pH.

- Buffering capacity is determined by:-

- (i) Concentration of the acid and the conjugate base, [𝐻𝐴]/[𝐴− ] the higher the

concentration of the higher the buffering capacity

[𝐻𝐴] [𝐻𝐴]
- The ratio of [𝐴− ]
: where the ratio [𝐴−] is unity the buffering capacity is maximum

1
- At this situation we expect: 𝑝𝐻 = 𝑝𝐾𝑎 + log 1

⇒ 𝑝𝐻 = 𝑝𝐾𝑎

Preparation of buffer

Buffer solution is prepare by choosing the acid or base and its salt whose

𝑝𝐾𝑎 in near the pH of interest. Suppose we want pH of around 8.0 we look for a base

whose pKa is around 8.0

Physiological buffers

1. Distilled H2O is buffer at pH = 8

2. Buffer system is found in the cell of living organism

Extracellular fluid

Major buffer in extracellular fluids or is 𝐻2 𝐶𝑂3 / 𝐻𝐶𝑂3− 𝑝𝑘𝑎 = 6.5

Intracellular fluid

Major buffer in intracellular fluid is 𝐻𝑃𝑂4− / 𝐻𝑃𝑂42− 𝑝𝑘𝑎 = 7.2

Exercise: 3.28g of sodium (I) ethanoate are dissolved in 1dm3 of 0.01 molar 𝐶𝐻3 𝐶𝑂𝑂𝐻

solution. What is the pH of the resulting solution given that 𝑝𝑘𝑎 for ethanoic acid =

1.84x 10-5 mol dm-3

𝐻 = 1, 𝐶 = 12, 𝑂 = 16, 𝑁𝑎 = 23 𝑝𝑘𝑎 = 6

[𝐻𝐴]
Soln:- 𝑝𝐻 = 𝑝𝑘𝑎 − log [𝐴−] **

[𝐴𝑐𝑖𝑑]
[𝐻 + ] = 𝑘𝑎 𝑥
[𝑆𝑎𝑙𝑡]

But 1 mole of CH3 COONa = 82g.

No. o f moles of CH3COONa = 3.28/82 = 0.04mole

[0.01]
[𝐻 + ] = 1.84 𝑥 10−5 𝑥 = 4.6 𝑥 10−6 𝑚𝑜𝑙/𝑑𝑚3
[0.04]

−log[𝐻 + ] = − log 4.6 𝑥 10−6

𝑝𝐻 = 5.34 (Also try the use of log in solving this problem from the initial stageusing

equation **)

𝑨𝑷𝑷𝑳𝑰𝑪𝑨𝑻𝑰𝑶𝑵 𝑶𝑭 𝑨𝑪𝑰𝑫 𝑩𝑨𝑺𝑬 𝑻𝑰𝑻𝑹𝑨𝑻𝑰𝑶𝑵

1. Made use of in elemental analysis, element susceptible TO THIS TYPE OF

ANALYSIS ARE NON METALLIC e.g. C, N, Cl, Br, S, P, etc.

2. In determination of inorganic substances e.g ammonium salts using Kjedahl

method; nitrate, nitrites, carbonate and carbonate mixtures.

3. Use in detection of organic functional groups. E.g –COOH,

4. In the determination of salts.