Principles of Titrimetric Analysis

Principles of titrimetric analysis
• Titrimetric method
• An analysis method in which:
the volume of a solution of known concentration consumed during an analysis is
taken as a measure of active constituent in a sample being analyzed
Titrimetric methods
Volumetric Gravimetric Coulometric
the quantity of charge

the volume of the the weight of the in coulombs required
standard reagent is standard reagent is to complete a reaction
the measured quantity the measured quantity with the analyte is the
quantity
Definition of terms
• Titration. the process of adding and then actually measuring the volume of titrant
consumed in the assay. This volume is usually measured by the help of a calibrated
burette.
• Titrant. The solution of known strength employed in the assay.
• Analyte/Titrand. Chemical entity under assay
• Indicator. a chemical substance sensitive enough to display an apparent change in
color very close to the point in the ongoing titration process at which equivalent
quantities of analyte and titrant have almost virtually reacted with each other.
• Endpoint. Which where there occurs a sudden change in some property of the
reaction mixture made apparent by the use of an indicator
Stoichiometric point vs End point
• Stoichiometric point
the theoretical point at which
equivalent amounts of the titrant
and analyte have reacted1
• End point
the point where titration stops; at
which there occurs a sudden
change in some property of the
reaction mixture2
standard solutions
• Standard solution. a solution of known (pre-determined) concentration
- Primary standard. the substance of known purity whose carefully weighed
quantity helps in the standardization of an unknown solution
- Secondary standard. another standard solution that is used for standardization
of an unknown solution.
• Standardization. the actual determination of either the normality or the molarity of a

solution
Standardization of an unknown solution of HCl
A. By using analytical grade Na2CO3, and
B. By using a standard solution of NaOH
Primary standard
• Characteristics of a primary Examples of Primary Standards
standard: • Sodium carbonate
• High purity Na2CO3
• Stable in air • Potassium biphthalate
• Absent of hydrated water molecules KHC8H4O4
• moderate cost and easily available • Potassium dichromate

K2Cr2O7
• soluble in titration solutions
• Sodium oxalate
• large formula (molecular) weight
Na2C2O4
Primary vs Secondary standard
Primary Standard Secondary standard

• made from primary standard substances • Made specifically for a certain analysis
• Extremely pure (about 99.9%) • Not very pure
• Less or not reactive • Comparatively more reactive
• Not hygroscopic • Somewhat hygroscopic
• Used to standardize secondary standards • Used for specific analytical experiments
and other reagents
Desirable properties of a standard solution
• the solution is stable and does not require standardization before use
• reacts quickly with the analyte
• the reaction with the analyte is complete and a good endpoint is observed
• the reaction with analyte is selective and described by a simple, balanced equation
Types of titration methods
Direct Titration Residual/Back titration

conducted by introducing a titrant gradually require the addition of a measured standard
from a burette into a solution being assayed solution (excess in amount) to the analyte,
until chemically equivalent amount have the excess is then being titrated with another
reacted standard solution
Direct vs Residual titration
Direct Residual/Back
Reactions One chemical reaction occurs Two chemical reactions occur
Titration Done between a known and an Done between two known compounds
unknown compound
Analyte Is the unknown compound The remaining amount of the reagent
added in excess
Applicati Used when the endpoint of the titration Used to determine the exact endpoint
ons can easily be obtained when there are sharp color changes
back titration is often preferable if
• One of the reactants is volatile and some might escape during the titration
(e.g NH3)
• the analyte is an insoluble salt (e.g CaCO3)
• a particular reaction is too slow
• direct titration would involve a weak acid-weak base titration
Chemical reactions used in titrimetry
Neutralization Oxidation-
(acid-base) reduction
Precipitation Complexation
Requirements for titrimetric analysis
Regardless of the type of reaction used, four requirements must be met if the reaction
is to be used for titrimetric analysis:
1. The reaction must proceed to completion
2. The reaction must proceed in a stoichiometric manner
3. A suitable end-point-detecting device (indicator) must be available
4. Reactions must be rapid to obtain a discernible, sharp end-point
How to know if a reaction has proceeded to completion?
• Formation of a slightly dissociated substance as a reaction product
• removal of one or more of the products of the reaction as a gas
• removal of one or more of a product of reaction as a precipitate
• removal of an ionic substances such as a complex ion
Indicators
Complex organic compounds used
• To determine the end points in neutralization reactions,
• To determine [H+] or pH, or
• to indicate that a desired change in pH has been effected
Theories on the color change of indicators
• Physicochemical theory
- attributes the color to certain ions an increase in which causes the appearance
of a new color, and a decrease in which causes the disappearance of a color or
the appearance of a different color
• Organic theory
- attributes the color to certain groupings of elements in a compound, and the
change in color to a change in molecular structure
• Colloidal theory
- assumes that indicators form colloidal solutions the change in color of which is
dependent upon change in size of the colloidal particle
How do we know what is a ‘good indicator’?
• produces a sharp contrast between the two colors it exhibits in acid and alkaline
mediums
• color change takes place over a very small range of pH values (sensitivity)
Calculations in volumetric analysis
Definition of terms
• gram equivalent weight (GEW). the weight in grams which is chemically
equivalent to 1 gram-atom of hydrogen (1.0079 g).
• Equivalent. The number of gram-equivalents involved in a quantitative procedure.
• Normality. An expression of concentration; the number of equivalents of solute per
liter (eq/L) or milliequivalents per milliliter (meq/mL).
• Molarity. An expression of concentration; the number of moles of solute per liter
(mol/L) or millimoles per milliliter (mmol/mL).
• Titer. The weight of a substance chemically equivalent to 1 mL of a standard
solution.
• Milliequivalent factor (meq wt). The weight of substance chemically equivalent to
1 mL of a 1 N solution.
Formulas to remember
Normality equivalents of solute
=
volume of solution in liters
= molarity (M) x equivalence factor (f)

Equivalence weight of solute (g)
(GEW) =
EW
Equivalence Molecular weight of solute (g/mol)
=
weight # Eq/mol
Equivalence Factor (f)
Equivalence factor (f) Example

Acid number of H+ ions HCl = 1; H2SO4 = 2; H3PO4 = 3
Base number of OH- ions NaOH = 1; Ba(OH)2 = 2; Al(OH)3 = 3
Salt total valence NaCl = 1; ZnCl2 = 2
Redox total oxidation no. change
net electrons transferred
Let’s try this!
What is the normality of the following?
1. 0.1381 M NaOH
2. 0.0521 M H3PO4
3. 0.5781 g acid (meq wt = 0.1873) in 250 mL of solution
4. 0.321 g sodium carbonate in 250.0 mL of solution

• Standardization
Primary standardization
a pure, dry chemical GEW wt sample
OR
V meq ×vol
Secondary Standardization
Solution of accurately known N1V1 = N2V2
concentration
Let’s try this!
1. If 25.00 mL of citric acid solution is
titrated with 28.12 mL of 0.1718 N
KOH, what is the concentration of
citric acid? N1V1 = N2V2
2. If 31.87 mL of a base was required (28.12 mL)(0.1718 N) = (N2)(25.00

in the standardization of 0.4258 of mL)
potassium biphthalate (KC8H5O4; N2 = [(28.12 mL)(0.1718 N)]/(25.00
eq wt = 204.23), what is the mL)
normality of the base?
N2 = 0.1932 N
3. What is the normality of an acid if
21.18 mL was needed to titrate
0.1369 g of Na2CO3?
Let’s try this!
citric acid?
wt substance
2. If 31.87 mL of a base was required N=
meq ×vol
in the standardization of 0.4258 of
0.4258 g
potassium biphthalate (KC8H5O4; N=
0.20423 × 31.87 mL
eq wt = 204.23), what is the
N = 0.6542 N
0.1369 g of Na2CO3?
Let’s try this!
citric acid?
wt substance
2. If 31.87 mL of a base was required N=
meq ×vol
in the standardization of 0.4258 g
0.1369 g
of potassium biphthalate (KC8H5O4; N=
? × 21.18 mL
eq wt = 204.23), what is the
N = 0.1212 N
0.1369 g of Na2CO3?
Purity
(%w/w or %w/v)
let’s try this!
What is the purity acidity (%) of a sample (eq wt = 173.8) if 20.07 mL of 0.110 N of the
base was consumed to neutralize 0.7231 g of the sample ?
chemical reactions used in titrimetry
Neutralization Oxidation-
(acid-base) reduction
Precipitation complexation
End of Principles of Titrimetry
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Principles of titrimetric analysis

Volumetric Gravimetric Coulometric

the quantity of charge

• Standardization. the actual determination of either the normality or the molarity of a

• moderate cost and easily available • Potassium dichromate

Primary Standard Secondary standard

Direct Titration Residual/Back titration

= molarity (M) x equivalence factor (f)

Equivalence factor (f) Example

3. 0.5781 g acid (meq wt = 0.1873) in 250 mL of solution

4. 0.321 g sodium carbonate in 250.0 mL of solution

2. If 31.87 mL of a base was required (28.12 mL)(0.1718 N) = (N2)(25.00

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