Titrimetric Methods of Analysis

 based upon measuring the amount of

reagent of known concentration (SR) that is
consumed by the analyte (A)
a A + b SR -- In  c P

 widely used for routine analyses because

they are rapid, convenient, accurate and
readily automated
 Titrimetric Methods of Analysis

1. Volumetric Titrimetry involves measuring the volume of a

solution of known concentration
that is needed to react essentially
completely with the analyte

2. Gravimetric Titrimetry differs only in that mass of the

reagent is measured instead of its
volume

3. Coulometric Titrimetry the “reagent” is a constant direct

electrical current of known
magnitude that directly or indirectly
reacts with the analyte; the time
required to complete the
electrochemical reaction is
measured
 Advantages of Weight Titrations

1. Calibration of glassware and tedious

cleaning to ensure proper drainage is
avoided.
2. Temperature corrections are unnecessary.
3. Weight measurement can be made with
considerably greater precision and
accuracy.
4. Weight titrations are more easily
automated.
 Volumetric Titrimetry

Titration
 performed by slowly adding
a standard solution from a  Equivalence Point
buret to a solution of the amount T = amount A
analyte until the reaction
between the two is judged  End Point - a physical
complete
change associated with the
 volume of reagent needed to condition of chemical
complete the titration is equivalence occurs during
determined from the
difference between the titration
initial and final volume
readings  Et = Veq - Vep
 Volumetric Titrimetry
Indicator
 often added to the analyte
solution in order to give an
observable physical change
(the end point) at or near
the equivalence point
 typical indicator changes:
appearance/disappearance
of color, a change in color,
appearance/disappearance
of turbidity
 instruments to detect end
points: voltmeters,
ammeters, ohmmeters,
colorimeters, temperature
recorders and
refractometers
 weaker than the analyte,
kept at a minimum
amount, intensely colored
and react last with the
titrant
 Volumetric Titrimetry

Primary Standard Characteristics:

 a highly purified  high purity

compound that serves  stability toward air
as a reference material  absence of hydrate water
in all volumetric  ready availability at
methods modest cost
 accuracy of a method  reasonable solubility in
is critically dependent the titration medium
on the properties of  reasonably large molar
this compound mass
 Volumetric Titrimetry

Secondary Standard Characteristics:

 standard solution /  be sufficiently stable

standard titrant  react rapidly with the
analyte
 a reagent of known
 react more or less
concentration that is
completely with the
used to carry out a
analyte
titrimetric analysis
 undergo a selective
 expressed in terms of reaction with the
molarity and normality analyte
 Methods for Establishing Concentration
of Standard Titrants

A. Direct Method B. Standardization

 carefully weighed quantity 1. weighed quantity of a

of a primary standard is primary standard
dissolved in a suitable
solvent and diluted to an 2. measured volume of
exactly known volume in a another standard
volumetric flask solution/secondary
standard
 Types of Titration Methods
1. Direct Titration 2. Indirect Titration
Method Method
 titrant reacts directly  Replacement Titration
with analyte/standard Method
 employs a preliminary
 a simple relationship
exist between the titrant reaction in which the
used and the analyte/standard is
analyte/standard replaced by an equivalent
present amount of another
substance which is then
determined by titration
 Types of Titration Methods
3. Back-Titration
Chemical Equations:
Method
 Residual Titration Method  Direct Titration:
aA + bT In  cP
 a known excess of the
 Indirect Titration:
titrant is added to the
aA + b R  c NS
analyte/standard solution
d NS + e T In f P
 amount of analyte is  Back-Titration:
found by difference
aA + b T1  c P
excess
d T1 + e T2 In fP
excess
Classification of Volumetric Methods

1. Acid-Base 2. Precipitation

 many compounds, both  the titrant forms an insoluble

inorganic and organic, are product with the analyte
either acids or bases and can be
titrated with a standard  indicators can be used to detect
solution of a strong base or a the end point or the potential of
strong acid the solution can be monitored
electrically
 end points of these titrations
are easy to detect, either by
means of an indicator or by
following he change in pH with
a pH meter
Classification of Volumetric Methods

3. Complexometric 4. REDOX

 the titrant is a reagent that  involves the titration of an

forms a water-soluble complex oxidizing agent with a reducing
with the analyte, a metal ion agent or vice-versa

 the titrant is often a chelating  there must be a sufficiently

agent ; EDTA large difference between the
oxidizing and reducing
 reverse titration may be carried capabilities
out also
 end points detected by
 indicators can be used to form appropriate indicators or by
a highly colored complex with various electrometric means
metal ion
 Exercise 6
Assay of Table Wine
A 25.00-mL sample of Sample White Table Wine
white table wine was Analyte H2C4H4O6
diluted to about 100-mL
and titrated with 28.40- Indicator Phenolphthalein
mL of 0.05412-N NaOH Titrant NaOH
with phenolphthalein Method Volumetric Titrimetry
as indicator. Express the
Reaction Acid-Base Reaction
acidity of the wine in
terms of grams of Titration Direct Titration Method
tartaric acid Method
(H2C4H4O6) per 100 mL. Given:
25.00-mL sample
Molar Masses: 28.40-mL of 0.05412-N NaOH
H2C4H4O6 = 150.09 Answer: 0.4614 g /100 mL
NaOH = 40.00
 Exercise 6

Standardization of HCl
Exactly 50.00-g of HCl Analyte HCl
required 29.71-g of Standard Ba(OH)2
0.01963-Mw Ba(OH)2 to Indicator Bromocresol Green
reach an end point with Method Weight Titrimetry
bromocresol green Reaction Acid-Base Reaction
indicator. Calculate the Type of Standardization & Titration Method
weight molarity of the Secondary Standardization
HCl solution. Direct Titration Method
Given:
Molar Masses: 50.00-g HCl
HCl = 36.46 29.71-g 0.01963-MW Ba(OH)2
Ba(OH)2 = 171.36 Answer: 0.02333-MW
 Exercise 6
A sample of copper Assay of Copper Ore
ore weighing 2.132-g is Sample Copper Ore
dissolved in acid and Analyte Copper
the copper is Method Coulometric Titrimetry
electrolyzed: Reaction Redox Reaction
Cu 2+ + 2 e-  Cu Given:
If 8.04-min is required 2.132-g sample
for the electrolysis using 8.04-min - 2.00A
a constant current of Answer: 14.9%
2.00-A, calculate the
percentage of copper
in the ore.
Molar Mass: Cu = 63.54