T I T R I M E T R I C A N A LY S I S
CHAPTER 4
• S TA N D A R D S
•DILUTION &
S T A N D A R D I Z AT I O N
TITRIMETRIC ANALYSIS
• Volumetric analysis- titrimetric analysis is one of the quantitative
of chemical analysis that involves the measurement of the volume
solution of known concentration which is required to react with the
analyte.
• A titrimetric method of analysis is based on a chemical reaction
• where n molecules of the reagent, Y, and m molecules of the
react.
• The reagent Y in solution is called standard solution and its
is determined by the process of standardization.
STANDARDS
• A reagent solution of ACCURATELY
KNOWN CONCENTRATION is called a
STANDARD SOLUTION.
Primary standard
Highly purified compound that serves as a reference
material in all volumetric/titrimetric method.
STOCK SOLUTION
• A concentrated solution that will be diluted to
some lower concentration for actual use. Stock
solutions are used to save preparation time,
conserve materials, reduce storage space and
improve the accuracy with which working solutions
are prepared.
Working Solution
• A name given to a chemical solution made for
actual use in the lab, usually made from diluting
stock or standard solutions.
PROPERTIES OF PRIMARY STANDARD
MATERIAL/REAGENT
1. Must exhibit HIGH PURITY, typically 100±0.05 %.
2. Must exhibit HIGH STABILITY, preferably for years
under proper storage conditions. It must be stable with
respect to both spontaneous decomposition and
reaction with moisture or air.
3. Preferably should not contain water of hydration
(hygroscopic).
4. High equivalent weight (more stable) is preferable
when used for standardization.
5. Must not be costly.
6. Should be easily available.
7. Must be readily soluble.
PREPARATION OF STANDARD
SOLUTION
•A PRIMARY standard solution can be prepared by dissolving
an accurately WEIGHED amount of the solid reagent.
•Usually a PRIMARY STANDARD in a SOLVENT and
diluted to an accurately KNOWN VOLUME of solution using
volumetric flask.
•Solution prepared using the primary standard will give primary
standard solution.
PROCESS OF MAKING A STANDARD
SOLUTION FROM SOLIDS
DILUTION
– Adding solvent to a solution
– Adding solvent results in a solution of lower
concentration.
– Concentration of a solution can be calculated by
applying this equation: MaVa = MbVb
– Where M is molarity, V is volume, and the subscripts
a and b refer to the concentrated and diluted values.
Example:
How many mL of 5.5 M NaOH are needed to prepare 300 mL
of 1.2 M NaOH?
Solution:
5.5 M x V1 = 1.2 M x 0.3 L
V1 = 0.065 L = 65 mL
• So, to prepare 1.2 M NaOH solution, pour 65 mL of 5.5 M
NaOH into the container and add water to get 300 mL final
volume.
STANDARDIZATION
• A process to determine the concentration of a solution by
titrating with a primary standard or with a solution of known
concentration.
• Example:
1) Accurately weigh out 1.325 g of Na2CO3 and dissolve it in a little
water, then add enough water to fill a 250 mL volumetric flask.
2) This solution would then be used to standardized the HCl acid.
This will give a very accurate determination of the concentration
of the HCl solution.
3) This is how the HCI solution has been standardized, and can
subsequently be used to accurately determine the concentration of
a base solution.
2HCl(aq) + Na2CO3(aq)→2NaCl(aq) + H2O(l) + CO2(g)
Standardization
➢Required when a non-primary titrant is used
- Prepare titrant with approximately the desired
concentration
- Use it to titrate a primary standard
- Determine the concentration of the titrant
- Reverse of the normal titration process!!!
Titration Standardization
titrant known titrant unknown
concentration concentration
analyte unknown
analyte known
concentration
concentration
Primary standards
• Oxalic acid, H2C2O4.2H2O
• Calcium carbonate, CaCO3
• Sodium chloride, NaCl
• As2O3
• C8H5KO4
• Potassium duhydrogen phosphate,
KH2PO4
• KC4H5O6
SECONDARY
STANDARD
•Examples:
HCl, HNO3, NaOH, KMnO4, and AgNO3.
ACID-BASE
TITRATION
ACID BASE THEORY
Arrhenius
• Acid: Substances that contain hydrogen (H) and produces H+
in aqueous solutions.
• Example: HCl, HNO3
• Base: Substances that contain the hydroxyl (R-OH) and
produces OH- ions in aqueous solutions
• Example: NaOH, Ca(OH)2
Bronsted
• Acid: Can donate proton, H+
• Base: Can accept proton, H+
STRENGTH OF ACID & BASE
• The strength of an acid or base depends on the
degree of dissociation of the acid or base in
water.
Strong acid Weak acid
Dissociates completely Dissociates partially
Produce high Produce low
concentration of H+ ions concentration of H+ ions
Example: HCl, HBr, HI, Example: H3PO4,
HNO3, H2SO4 CH3COOH
Strong base Weak base
Dissociates completely Dissociates partially
Produce high Produce low
concentration of OH- concentration of OH-
ions ions
Example: NaOH, KOH, Example: NH3, CH3NH2,
Ca(OH)2, Ba(OH)2, C2H5NH2
INDICATOR AND CHOICE OF INDICATOR
Acid - Base Indicators
• The acid-base indicator function by
changing color just after the equivalence
point of a titration. This color change is
called the end point.
• The end point is most often detected
VISUALLY. Most acid-base indicators
are organic dye molecules which are
either acids or bases.
ACID –BASE INDICATORS
• Indicators can be monoprotic (HIn) or diprotic (H2In) acids.
• The acid form of an indicator is usually colored. When it loses
a proton resulting in anion (In-), or base form of the indicator,
exhibiting different color.
HIn H+ + In-
(color A) (color B)
• A diprotic acid indicator, H2In, ionizes in TWO steps as follows:
H2In HIn- + H+ H+ + In-
(color A) (colour B) (colour C)
SELECTING AND
USING INDICATORS
➢Choose an indicator that undergoes a distinct color
change at the equivalence point (true end point).
➢Choose an indicator whose middle half of the pH transition
range (greatest color change) encompasses/overlap the pH
at the equivalence point or the pH at the steepest part of
the titration curve.
➢For indicator color change to be detectable by normal
eyesight, a rough tenfold excess of one or the other form of
the indicator must be present.
END POINT
• The point at which the reaction is observed to be completed.
• The end point in volumetric method of analysis is the signal that
tells the analyst to stop adding reagent and make the final
reading on the burette.
• End point is observed with the help of a suitable indicator.
Analyte + titrant equivalent point
then,
Indicator + titrant reacted indicator
Color 1 Color 2
This last step does not required all indicator be
converted – best only small percent need to be
reacted to make change visible.
EQUIVALENCE POINT
• The point at which an equivalent or
stoichiometric amount of titrant is added to
the analyte
• Theoretically at the equivalence point, the amount
of titrant that is required to react EXACTLY with
the amount of analyte present can be calculated.
• The volume of titrant required to just completely
react with the analyte is the TITER.
TITRIMETRIC ANALYSIS
• What is a titration :
• A procedure of carefully controlled addition of reagent
(titrant) to an analyte.
Usually in burette Known concentration Usually in a conical flask
TYPES OF ACID-BASE
TITRATION
❑Titration of strong acid with strong base
❑Titration of strong acid with weak base.
❑Titration of weak acid with strong base.
❑Titration of weak acid with weak base.
THE REQUIREMENTS FOR A
SUCCESSFUL TITRIMETRIC PROCEDURE
1. Reaction must be stoichiometric, well defined reaction
between titrant and analyte.
2. Sufficiently stable so that it is necessary to determine its
concentration.
3. Reaction should be rapid with the analyte so that the time
required between the additions of reagent is minimized.
4. React completely with the analyte so that satisfactory end
points can be achieved.
5. Reaction should have no side reaction, no interference
from other foreign substances.
6. Must have some indication of end of reaction, such as color
change or sudden increase in pH.
CHOOSING A TITRANT
• In theory, any strong acid or strong base can be used as
titrant.
• The reason for this is that most reaction involving a strong
acid or a strong base is QUANTITATIVE.
• Examples of strong acid titrants:
1. Hydrochloric acid (HCl)
2. Nitric acid (HNO3)
3. Perchloric acid (HClO4)
4. Phosphoric acid (H3PO4)
5. Sulfuric acid (H2SO4)
WEAK ACID TITRANT
1.Acetic acid (CH3COOH)
2.Ammonium ion (NH4-)
3.Hydrogen fluoride (HF)
4.Carbonic acid (H2CO3)
5.Nitrous acid (HNO2)
6.Hydrogen sulphide (H2S)
7.Hydrogen cyanide (HCN)
Strong base titrant Weak base titrant
Sodium hydroxide, NaOH Ammonium hydroxide,
NH4OH
Potassium hydroxide, KOH Amine acetate
Magnesium hydroxide, Carbonate, CO32-
Mg(OH)2
Barium hydroxide, Sodium carbonate, Na2CO3
Ba(OH)2
TITRATION CURVE
• A graph of pH versus volume of titrant added (the
solution in the burette) is called titration curve.
STRONG ACID VS STRONG BASE
❑ The graph is so steep at that point that there
will be virtually no difference in the volume of
acid added which ever indicator you choose.
You can see that neither indicator changes
colour at the equivalence point.
However, it would make sense to titrate to the
best possible colour with each indicator.
If you use phenolphthalein, you would titrate
until it just becomes colourless (at Ph 8.3)
because that is as close as you can get to the
equivalence point.
If you use methyl orange, you would titrate
until there is the very first trace of orange in the
solution. If the solution becomes red, you are
getting further from the equivalence point.
You can see that neither indicator changes colour at the equivalence
point.
STRONG ACID VS WEAK BASE
• This time it is obvious that
phenolphthalein would be
completely useless.
• However, methyl orange starts
to change from red to orange-
yellow very close to the
equivalence point.
• You have to choose an
indicator which changes color
on the steep bit of the curve.
STRONG BASE VS WEAK ACID
❖ This time, the methyl orange
is hopeless!
❖ Phenolphthalein changes
color exactly where you
want it to.
CALCULATION
•Mol = mass (g)
molar mass (g/mol)
•Molarity (M) = Mol
Volume (L)
• Mass (g )
= Liter (L) x Molarity [mol/L] x Molar Mass [g/mol]
aA + bB cC + dD
MaVa = a
MbVb b
CALCULATION ACID-BASE
Example:
A sample weighing 0.8365 g is a diprotic acid was dissolved in
75.0 mL distilled water. Indicator was added and the solution
was titrated with sodium hydroxide solution. 35.35 mL was
needed to reach the end point. Molar mass of acid is 150
gmol-1.Calculate the molarity of the base.
First write the reaction equation:
-
Equation: H2A + 2OH = 2H2O + A2-
• Mole acid = 0.835
150
= 5.5767 x 10-3 mole
• Molarity of acid = 5.5767 x 10-3 mol
0.075 L
= 0.0744 M
MaVa = 1 2 x 0.0744 x 75 = Mb
MbVb 2 35.35
Mb = 0.3157 M
• Example: Calculate the concentration of vinegar in
% w/v for a titration of 25 ml of vinegar which was
primarily diluted 10 times (25 mL into 250 mL),
reacted with 22.4 ml of 0.1 M NaOH standard
solution.
1)Write and balance the equation
CH3COOH + NaOH CH3COONa + H2O
2) Calculate mole of acid , n = Molarity (M) x Volume (Liter)
= 0.0896 (mol/L) x 0.250 L
= 0.0224 mol
3) Mass of acid (g) = molar mass x mol
= 60 g/mol x 0.0224 mol
= 1.344g
4) % w/v = (g/mL) x 100 = (1.344g/25 mL ) x 100 = 5.4%
PRACTICE 1
PRACTICE 2
PRACTICE 3
BACK TITRATION
BACK TITRATION
• A process in which the excess of a standard solution used to
consume an analyte is determined by titration with a second
standard solution.
• Example: Determination of acetylsalicylic acid in aspirin.
• Sometime direct titration of an analyte with a reagent is not
FEASIBLE. This is due to the following reason:
1. The reaction kinetics is slow or the rate of reaction is slow.
2. No suitable indicator in the direct titration.
3. The color change at the end point is slow or delay or not sharp.
4. The end point is far from the equivalence point.
5. Standard solution lacks stability.
EXAMPLE OF BACK
TITRATION
▪The titration of insoluble organic acid with NaOH is not
practical because the reaction is slow.
CH3COO-C6H4-COOH + 2NaOH CH3COONa + HO-
C6H4-COONa
▪ To overcome it, add NaOH in excess and allow the reaction
to reach completion and then titrate the excess NaOH with
a standard solution of HCl.
NaOH + HCl NaCl + H2O
▪ The system has gone from being ACID, past the equivalence
point to the BASIC side (excess base), and then back to the
equivalence point.
▪ The final titration to the equivalence point is called a
BACK TITRATION.
Back titration is applied when:
• Reaction is too slow.
• One of the reactants is volatile (NH3).
• Acid or base is an insoluble salt.
• Involve weak acid – weak base (no suitable
indicator).
EXAMPLE
150.0 mL of 0.2105 M nitric acid was added in excess to
1.3415 g CaCO3. The excess acid was back titrated with
0.1055 M NaOH. It required 75.5 mL of the base to reach
the end point.
Calculate the percentage (w/w) of calcium carbonate in
the sample.
2HNO3 + CaCO3 → Ca(NO3)2 + CO2 + H2O ----- 1
HNO3 + NaOH → NaNO3 + H2O ------- 2
From equations above:
2 mole HNO3 = 1 mole CaCO3
1 mole HNO3 = 1 mole NaOH
Initial amount of acid:
Mole of acid = 0.2105 x 0.150
= 0.031575 mole acid.
Remaining/excess acid during back titration:
Mol of excess acid = 0.1055 x 0.0755
= 7.965 x 10-3 mol
1 mol HNO3 = 1 mol NaOH
Mol of acid reacted with CaCO3 = (0.031575 – 7.965 x 10-3)
= 0.02361 mol
mol of CaCO3 = ½ x mole acid
= ½ x 0.02361
= 0.011805 mole CaCO3.
Gram CaCO3 = mole x molar mass
= 0.011805 x 100
= 1.1805 g
% CaCO3 = wt of CaCO3 x 100
wt of sample
= 1.1805 x 100
1.3415
= 87.99 % (w/w)
EXERCISE 2
