Titrimetric Methods  Solution:
Titrimetry
 Group of analytical techniques which takes advantage
of titers or concentration of solutions
 Refers to the use of a volume of solution with a known
concentration to determine the quantity of an analyte
 Titer – used to denote “equivalence”; the amount of a
solution required to complete a chemical reaction
Types of Titrimetry
 Volumetric Titrimetry
- Determines a quantity of an analyte using (1)
volumes of reagents with known concentration
and (2) the knowledge of the stoichiometry of the
reaction between the reagents and analytes.
 Gravimetric Titrimetry
- Determines the quantity of an analyte using a
mass of a solution of a known concentration.
 Coulometric Titrimetry
- Determines the quantity of an analyte by
measuring the number of coulombs or total
charge required to complete a reaction.
Important Calculation Concepts
 Calculation of concentrations
- Calculation of molarity
g g: grams of solute
M= MM MM: molar mass of solute
L L: liters of solution
- Dilution
C1: initial concentration
V1: initial volume
C1V1 = C2V2 C2: final concentration
V2: final volume
 Calculation of analyte concentration from titration
data
(M x mL) titrant = (M x mL) analyte (molar ratio)
Equivalence Point
 Point where enough titrant has been added to
stoichiometrically equivalent to the amount of analyte.
 Example:
50 mL of a 0.1 M AgNO3 solution would be required
to completely react with 0.005 moles of NaCl
End Point
 Point at which some detection/observation technique
tells you that chemical equivalence has been reached.
 Ideally, end point (observing) and equivalence point
(solving) should coincide but this rarely happens due
to the methods used to detect end point is prone to
slight error/alteration.
 The difference between equivalence and end point is
called as “titration error” or “over-titration”.
Primary Standard
 A high purity compound that serves as a reference
material in all volumetric and mass titrimetric method.
 Titrant must be of known concentration and ideally
should be made from a primary standard.
 Primary standard requirements
(High-StaAb-Dis-ReRe):
1. High purity.
2. Stability in presence of air.
3. Absence of any water of hydration (it varies with
changing humidity and temperature)
4. Dissolves readily (to produce stable solutions in
solvent of choice)
5. Relatively large molar mass (to minimize
weighing errors)
6. Reacts rapidly and stoichiometrically with
analyte
Secondary Standard
 Few materials meet all of the primary standard
requirements which is why a secondary standard is
commonly used in which they are standardized with
primary standards.
Standardization
 Process of determining the concentration of a
secondary standard with a high level of accuracy
through titration with a primary standard.
  Example of primary standards with their  Example C:
corresponding secondary standard: How much of the BaCl2 + 2H2O must be used to
prepare 1.00 liter of 0.500 M of Cl-? Assume BaCl 2
1: Potassium acid phthalate (KHP) completely dissociates.
2: Sodium hydroxide (NaOH)

1: Sodium carbonate (Na2CO3)

2: Hydrochloric acid (HCl)

Molarity (M)

 Number of moles of species dissolved in liters of

solution.

M = mol numbers of moles of solute

L volume of solution in liters

Normality (N)

 Number of equivalences of solute dissolved in liters of

solution

N = zM Equilibrium/Species Molarity (cM)

Where M is the molarity and z is the reaction
stoichiometric number  The number of moles of a specie at equilibrium in one
liter of solution. In order to compute calculate this, we
Analytical Molarity need to know something about the solute’s behavior in
the solvent.
 Total number of moles of a solute in one liter of
 Example A:
solution regardless of its chemical state.
Refer to Example A of Analytical Molarity
 Example A:
What is the equilibrium concentration of NaCl?
Find the analytical molarity of 117.0 g of sodium
Assume NaCl completely dissolve in solution.
chloride (NaCl) dissolved in 1.00 L of water.
 Solution:
MM NaCl = 58.5 g/mol
 Solution:

 Example B:
Weak acid, HA, is 5.00% dissociated in aqueous
 Example B: solution. What are the possible species and their
Find the analytical concentration of 294.0 g of sulfuric concentrations for a solution of HA with cM of 1.00
acid (H2SO4) dissolved in 1.00 L of water.
M?
MM of H2SO4 = 98.0 g/mol
 Solution:
 Solution:

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 What is the molar concentration of an aqueous ammonia (NH3)
solution with a density of 0.900 g/mL and 27% weight percent?

Percent Concentration

 Weight percent (w/w)

mass of solute x 100%
mass of solution

 Volume percent (v/v)

volume of solute x 100%
volume of solution

 Weight/volume percent (w/v)

mass of solute (g) x 100%
volume of solution (mL)

Density

 Expresses the mass of substances per unit volume. Its

SI units are g/mL or kg/L
 Density of water is approximately 1.00 g/mL at 40C What is the volume percent of ethanol (C2H6) in a solution
prepared by mixing 5.00 mL of ethanol with water to give 1.00
Specific Gravity
L of solution?
 The ratio of the mass of a substance to the mass of an
equal volume of water at a specified temperature,
commonly at 40C
 No unit or dimensionless

Examples:

What is the w/w % of an aqueous ammonia (NH3) solution at

14.3 M with a density of 0.900 g/mL?
Volumetric Calculations: Titration Data Advantages of Weight Titration

 Problem: the molarity of the NaOH titrant is known 1. Calibration of glassware and pipette
and we want to find the molarity of the HCl solution, 2. Temperature independence
our analyte. 3. Greater precision and accuracy readily measured at
 Solution: take a known volume of the HCl solution +0.1 mg
measure the volume of NaOH used to react completely 4. More easily automated than volumetric titration
with the HCl. It is usually done in many trials and the
Disadvantages of Weight Titration
results are averaged.
 NaOH + HCl NaCl + H2O 1. Relatively elaborate/expensive equipment
- Mole NaOH = Mole HCl 2. Tedious
- C NaOH x V NaOH = C HCl x V HCl 3. Time-consuming sometimes
- Mole NaOH = C NaOH x V NaOH
Mole HCl C HCl x VHCl
 Example:
The titration of 50.00 mL of an unknown
concentration of H2SO4 with standardized base
required 25.00 mL of 0.1000 M NaOH. What is the
unknown concentration of H2SO4?

Weight Titrations

 In this technique, the volume of titrant delivered is

weighed and the moles delivered calculated from the
“weight molarity”.
 C weight = Number of moles of solute (mole)
Weight of Solution (kg)