Vous êtes sur la page 1sur 13

Basics of

Volumetric Analysis
(aka Titrations)
Related Reading (Harris, 5th Ed.)
6.1 6.3
9.3 9.6
10.4

Volumetric Analysis

Review of Titrations
A titration is any procedure where increments of a known reagent solution (the titrant)
is added to a solution containing an unknown amount of the analyte until the reaction is
complete, called the equivalence point:

Because the equivalence point is based on the stoichiometry of the neutralization


reaction

the volume of titrant required to reach the equivalence point in an acid-base


titration does not depend on whether the acid is strong or weak.

In practice, the measured end of a titration is called the endpoint.


2

Volumetric Analysis

Types of Titrations
There are two categories of titrations
direct titration:
back titration:

Titrations can also be categorized by the means of measurement:

Observing the color change of an


indicator

Monitoring the change in voltage or


current between two electrodes

Monitoring the change in pH of the


solution

Monitoring the absorbance of light by


species in the reaction

Indicators are usually used in acid-base or precipitation-based titrations, although


they also can be used in redoximorphic or complexation-based titrations.

Volumetric Analysis

Example

Volumetric Analysis

Standards and Standardization


A standard solution is
The validity of a titration depends on the accuracy of the known concentration of the
titrant. Ideally, it should be a primary standard

Alternately, a titrant may be standardized by measuring the concentration (and


associated error) of the prepared titrant, regardless of source, if a primary standard is
not available. A standard of this type is referred to as a secondary standard.

In fact, any standard solution is

=
5

Volumetric Analysis

Detecting the End Point


The equivalence point and the endpoint are NOT the same!!!
(And the terms are not interchangeable)
The difference between the endpoint and the equivalence point is called titration
error and can be estimated

If too much indicator is added in a titration, interactions with the indicator can become
significant and indicator error can be introduced.
The endpoint of a titration is generally found using an indicator. Indicators are either

They are added at such low concentration that they have no direct effect on any
equilibrium or redoximorphic state in solution but greatly affect the color of the
solution.
On a fundamental level, indicators act in a manner similar to buffers!
6

Volumetric Analysis

Acid/Base Indicators

Thymol Blue

Most acid-base indicators are weak organic acids or bases whose various protonated
species have different colors.

pH
pH indicators act as buffers in response to pH changes, only showing a clear color
change over the effective range of the buffer (1 pH unit).
7

Volumetric Analysis

pH Indicators
The closer the pKa of an indicator is to the pH at the equivalence point of the titration,
the smaller the titration error
Low pH
Color

Transition
pH range

High pH
Color

Low pH
Color

Transition
pH range

High pH
Color

Methyl violet

yellow

0.02.0

blue-violet

Bromocresol purple

yellow

5.26.8

purple

Leucomalachite green

yellow

0.0-2.0

green

Bromothymol blue

yellow

6.07.6

blue

Thymol blue

red

1.22.8

green

Neutral red

red

6.88.0

yellow

Methyl yellow

red

2.94.0

yellow

Phenol red

yellow

6.88.4

red

Bromophenol blue

yellow

3.04.6

purple

Cresol Red

yellow

7.28.8

redpurple

Congo red

blueviolet

3.05.0

red

colorless

7.38.7

greenblue

red

3.14.4

orange

yellow

8.09.6

blue

yellow

3.85.4

blue

Phenolphthalein

colorless

8.310.0

fuchsia

Methyl red

red

4.46.2

yellow

Thymolphthalein

colorless

9.310.5

blue

Litmus

red

4.5-8.3

green

Alizarine Yellow R

yellow

10.212.0

red

Azolitmin

red

4.58.3

blue

Leucomalachite green

green

11.614

colorless

Indicator

Methyl orange
Bromocresol green

Indicator

Naphtholphthalein
Thymol blue

Volumetric Analysis

Other Common Indicators


Two other types of indicators that rely on color are:
Complexation
indicators:
Eriochrome Black T

Consider the use of thiocyanate (SCN-) as a complexation indicator for the presence of
free Fe3+ ions in solution:

3+ + +

Volumetric Analysis

Other Common Indicators


Adsorption
indicators:

Charged dyes (typically anionic) that are attracted to an


oppositely charged ionic atmosphere around the precipitate.

Dichlorofluorescein
+ charged
ionic atmosphere

Adsorbed DCF

+ +

+
+

+
+

AgCl

Free
DCF

+ + +

Often, both of these types of indicators are also pH sensitive with amphiprotic forms,
so pH must be carefully controlled when used.
10

Acid/Base Chemistry

Slightly Off Topic:


Planning a Buffer Theory
To prepare 500 mL of a 0.10 M acetate buffer at pH 5.00
Method #1: Direct
From a weak acid and its conjugate base
(using 0.10 M HC2H3O2 and 0.10 M NaC2H3O2)

Method #2: Indirect


From a weak acid and a strong base
(using 5.0 M HC2H3O and 1.0 M NaOH)

Note: It is also possible to use a weak base and its conjugate acid (or a strong acid) to make a buffer.

11

Acid/Base Chemistry

Preparing a Buffer The Real World


I followed my calculationswhy isnt doesnt my buffer have the right pH?
The pH of a buffer is dependent on the temperature and ionic strength of the solution!

So how do I avoid this problem?


1. Allow all solutions, solids and glassware to come to room temperature!
2. Measure out all solids and solutions into a volume about 80% of the final desired
volume.

3. Using a pH meter, adjust the pH to the desired value with small volumes of 1 M
NaOH or 1 M HNO3.
4. Transfer the buffer to a volumetric flask (along with rinse from any containers) and
bring to the desired volume.
12

Volumetric Analysis

Example - Group Practice

13

Vous aimerez peut-être aussi