Titrimetric analysis- additional notes

Titration is a sensitive analytical method that lets you determine an unknown concentration of a chemical in
solution by introducing a known concentration of another chemical. Several factors can cause errors in
titration findings, including misreading volumes, mistaken concentration values or faulty technique. Care
must be taken as the solution of the known concentration is introduced into a specific volume of the
unknown through laboratory glassware such as a burette or pipette. Indicators are used to determine when a
reaction has come to an end.

End Point Error

The end point of a titration is when the reaction between the two solutions has stopped. Indicators, which
change color to indicate when the reaction has stopped, do not change instantly. In the case of acid-base
titration, the indicator may first lighten in color before changing completely. Also, each individual perceives
color slightly differently, which affects the outcome of the experiment. If the color has changed slightly, too
much of the titrant, which comes from the burette, can be introduced into the solution, overshooting results.

Misreading the Volume

The accuracy of titration requires precise measurement of the volume of materials in use. But ma rkings on a
burette can be easily misread. One way to misread the volume is by looking at the measurement on an
angle. From above, it can seem like the volume is lower, while from below, the apparent volume looks
higher. Another source of measurement error is looking at the wrong spot. A solution forms a concave
curve and the bottom of the curve is used to measure the volume. If the reading is taken from the higher
sections of the curve, the volume measurement will be in error.

Concentrations

Errors in concentrations directly affect the measurement accuracy. Errors include using the wrong
concentration to begin with, which can occur from chemical decomposition or evaporation of fluids. The
solution may have been prepared incorrectly or contaminatns could have been introduced into the solution,
such as using dirty equipment. Even the process of cleaning your equipment, if carried out with the wrong
solution, can affect the concentrations of the solutions to be experimented on.

Using the Equipment Incorrectly

You must follow strict guidelines in handling and using all equipment during the experiment as the slightest
mistake can create errors in the findings. For example, swirling the solution can result in loss of solution that
will affect results. Errors in filling the burette can cause air bubbles that affect the flow of the liquid in the
burette.

Other Errors

Other human or equipment errors can also creep in. Human error includes using selecting the wrong
reagents or using the wrong amount of indicator. Equipment error typically is in the burette, which can
develop leaks over time. Even a small loss of fluid will affect the results of the titration.

Preparation of a Primary Standard Solution of Sodium Carbonate

This section describes the procedure for preparing 250.00 mL of 0.04906 mol L-1 standard solution of sodium
carbonate.

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Step 1. Place a small amount of distilled water into a clean, dry, 250.00 mL
volumetric flask.
volumetric
flask
Step 2. Weigh out 1.300 g of the anhydrous sodium carbonate prepared above
onto a clean dry watch glass or small beaker. Weigh by difference.
Dissolve solid in approximately 50cm3 in a beaker.

Step 3. Position a clean, dry glass funnel into the neck of the volumetric flask.

Step 4. Pour the solution into the volumetric flask. Rinse beaker and funnel with
distilled water, into the volumetric flask.
funnel placed in
volumetric flask with
air gap
Step 5. Pour distilled water through the funnel slowly until the water level in the
volumetric flask reaches the base of the neck.
Step 6. Remove the funnel from the volumetric flask.
Step 7. Use a pasteur pipette to transfer distilled water drop by drop to the
volumetric flask until the bottom of the meniscus sits on the graduation
mark on the neck of the volumetric flask when viewed at eye level.
Step 8. Stoppper the volumetric flask and invert it several times to ensure
thorough mixing.
reading from bottom
of mensicus

Standardization of a solution of KMnO4 with oxalic acid

The titration of potassium permanganate (KMnO4) against oxalic acid (C2H2O4) is an example of redox
titration. In close proximity to the endpoint, the action of the indicator is analogous to the other types of visual
colour titrations in oxidation-reduction (redox) titrations.

Theory:
Potassium permanganate is a strong oxidising agent and in the presence of sulfuric acid it acts as a powerful
oxidising agent. In acidic medium the oxidising ability of KMnO4 is represented by the following equation.
In acidic solution,
MnO4– + 8H+ + 5e– → Mn2+ + 4H2O
Solution containing MnO4– ions are purple in colour and the solution containing Mn2+ ions are colourless and
hence permanganate solution is decolourised when added to a solution of a reducing agent. The moment
there is an excess of potassium permanganate present the solution becomes purple. Thus KMnO4 serves as
self indicator in acidic solution.
Potassium permanganate is standardized against pure oxalic acid. It involves redox reaction. Oxalic acid is
oxidised to carbon dioxide by KMnO4 which itself gets reduced to MnSO4. Oxalic acid reacts with potassium
permanganate in the following way.
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The chemical reaction at room temperature is given below.
Reduction Half reaction:- 2KMnO4 + 3H2SO4 → K2SO4 + 2MnSO4 + 3H2O + 5[O]
Oxidation Half reaction:- 5(COOH)2 + 5[O] → 5H2O + 10CO2↑

Titration of potassium permanganate solution against standard oxalic acid solution:

1. Rinse the burette with the potassium permanganate solution and fill the burette with potassium
permanganate solution.
2. Fix the burette in the burette stand and place the white tile below the burette in order to find the end
point correctly.
3. Pipette out 10ml of 0.1M standard oxalic acid solution in a conical flask.
4. Add a test tube full of sulfuric acid in order to prevent oxidation of manganese to form manganese
dioxide.
5. Heat the mixture upto 60oC before titrating with potassium permanganate.
6. Note down the initial reading in the burette before starting the titration.
7. The hot solution is titrated against potassium permanganate solution and simultaneously swirl the
solution in the flask gently.
8. Initially the purple colour of KMnO4 is discharged with oxalic acid. The appearance of permanent
pink colour reveals the end point.
9. Repeat the titration until concordant values are obtained.
10. Note down the upper meniscus on the burette readings. Record the reading in the observation table
given below in order to calculate the molarity of KMnO4 given.

TITRATIONS WITHOUT INDICATORS

Conductiometric Titration

Conductometric titration is a type of titration in which the electrolytic conductivity of the reaction mixture is
continuously monitored as one reactant is added. The equivalence point is the point at which the conductivity
undergoes a sudden change. Marked increase or decrease in conductance are associated with the changing
concentrations of the two most highly conducting ions—the hydrogen and hydroxyl ions.[5] The method can be
used for titrating coloured solutions or homogeneous suspension (e.g.: wood pulp suspension[5]), which cannot
be used with normal indicators.
Acid-base titrations and redox titrations are often performed in which common indicators are used to locate
the end point e.g., methyl orange, phenolphthalein for acid base titrations and starch solutions for iodometric
type redox process. However, electrical conductance measurements can also be used as a tool to locate the
end point.
Example: titration of an HCl solution with the strong base NaOH. As the titration progresses, the protons are
neutralized to form water by the addition of NaOH. For each amount of NaOH added equivalent amount of
hydrogen ions is removed. Effectively, the mobile H+ cation is replaced by the less-mobile Na+ ion, and the
conductivity of the titrated solution as well as the measured conductance of the cell fall. This continues until
the equivalence point is reached, at which one obtains a solution of sodium chloride, NaCl. If more base is
added, an increase in conductivity or conductance is observed, since more ions Na+ and OH− are being added
and the neutralization reaction no longer removes an appreciable amount of H+. Consequently, in the titration
of a strong acid with a strong base, the conductance has a minimum at the equivalence point. The
conductometric titration curve is a plot of the measured conductance or conductivity values as a function of
the volume of the NaOH solution added. The titration curve can be used to graphically determine the
equivalence point.

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Potentiometric Titration
It is the procedure through which the quantity of the given test substance is determined by the measured
addition of titrant until the entire test substance undergoes reaction. After the titration process, the potential
difference between the two electrodes (namely the reference and indicator electrode) is measured in
conditions where a thermodynamic equilibrium is maintained and the current passing through the electrodes
does not disturb this equilibrium.

Potentiometric Titration Principle

Potentiometric titration is a laboratory method to determine the concentration of a given analyte. It is used in
the characterization of acids. In this method, there is no use of a chemical indicator. Instead, the electric
potential across the substance is measured.

Potentiometric Titration Method

Potentiometric Titration is done via the usage of two electrodes – an indicator electrode and a reference
electrode (generally a hydrogen electrode or a silver chloride electrode). One half-cell is formed with the
indicator electrode and the ions of the analyte, which is generally an electrolyte solution. The other half-cell is
formed by the reference electrode.
The overall cell potential can be calculated using the formula given below.
Ecell=Eind–Eref+Esol

The overall cell potential, Ecell is calculated in every interval where the titrant is measured and added. Now, a
graph is plotted with the Potential difference on the Y-axis and the volume on the X-axis as shown below.

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Endpoint is the midpoint of the steepest portion of the plot
It can be observed from the graph that the electric potential of the cell is dependant on the concentration of
ions which are in contact with the indicator electrode. Therefore, the Ecell is measured with each addition of the
titrant.

REDOX TITRATIONS

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