Pharmaceutical

Analytical chemistry
III
(SECTION 3, PART I)
 Titration
 It depends on the reaction between titrant (known concentration) and sample
(unknown concentration), in the presence of indicator (for e.g., DPA) to
determine the E.p.

 At the end of that reaction; the whole volume of the sample is consumed by a
volume of the titrant (of known conc.).

 The sample conc. is calculated by relating the volume of the titrant used to
neutralize the sample to (grams) of sample (using the equivalent factor (F)).

 i.e.; The output of the titration process is the determination of the sample
concentration.
 Equivalent factor (F)
 It represents the number of grams of sample which are equivalent to each 1 mL of the
titrant.

 It is calculated for the sample to convert the volume of titrant (E.p.) to grams of sample.

 i.e., each 1 mL of the titrant equivalent to how many grams of the sample ?

 For e.g., each 1 mL of 0.1 N KMnO4 (titrant) equivalent to 0.0152 gm of FeSO4 (sample).
This means that: F = 0.0152.

 To calculate the equivalent factor (F):

 To calculate the sample concentration we use the following equation:

𝑚𝑎𝑠𝑠
Concentration of sample =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 (𝑚𝐿)

E.P. × f × F × 𝟏𝟎𝟎𝟎
- Concentration of sample (gm / L) =
volume of sample (mL)

E.P. × f × F × 𝟏𝟎𝟎
- Concentration of sample (gm %) =
volume of sample (mL)

E.P. × f × F × 𝟏
- Concentration of sample (gm / mL) =
volume of sample (mL)
Where;

- f : is the correction factor of the titrant, which equals 1 for primary standards, and can be
obtained for secondary standards from standardization against primary standard, using the
following equation:

- F : is the equivalent factor calculated for the sample using the following equation, to convert
mL of titrant to grams of sample.
 Oxidation-Reduction reactions (Redox)
 Oxidation: it is a process which results in the loss of one or more electrons by atoms.
 Ex: Fe2+………………Fe3+

 Reduction: it is a process of gaining of one or more electrons by atoms.

 Ex: KMnO4………..MnSO4 (in acidic medium)

 Oxidizing agent: a substance that tends to oxidize other substance by being itself
reduced (gain electrons).
 EX: potassium permanganate, potassium dichromate, potassium iodate, Iodine,
and Potassium bromate

 Reducing agent: a substance that tends to reduce other substance by being itself
oxidized (lose electrons).
 EX: oxalic acid, oxalates, ferrous sulphate, and sodium thiosulphate
 Oxidation-Reduction reactions (Redox)
 Oxidation number: number of charges that the atom will have when it is
converted into an ion by either oxidation or reduction.

 Oxidation no. may have a +ve, –ve, or zero values & may be a fraction.
 The element may have more than one oxidation no.
e.g: Iron (Fe): Fe²⁺ (Ferrous, +2 ) and Fe³⁺ (Ferric, +3)
Manganese (Mn): MnO₂ (Manganese dioxide, +4), and KMnO₄ (Potassium
permanganate, +7)
 Oxidation-Reduction reactions (Redox)
Types of indicator (methods of E.P determination)
 pH Indicators
Ex: Phenolphthalein, and Methyl orange
 Precipitation Indicators
Ex: Potassium chromate
 Complexometric Indicators
Ex: Eriochrome Black T, and Murexide
 Self Indicator
Ex: Potassium permanganate
 Internal Redox Indicators
Ex: Diphenylamine
 Specific Indicator
Ex: Starch
 Methods of E.p determination in redox titrations

Self indicator titrant Redox indicator

Ex: KMnO4 Ex: Diphenylamine

(DPA)

Specific indicator

Ex: Starch
Determination of Ferrous sulphate (FeSO4) sample

Using potassium dichromate (K2Cr2O7) as a titrant &

• Diphenylamine (DPA) redox indicator.

Using potassium permanganate (KMnO4) as a titrant

• Self indicator.
Determination of Ferrous sulphate (FeSO4) by potassium
permanganate (KMnO4)
 Equation
10 FeSO4+ 2 KMnO4 + 8 H2SO4 5 Fe2(SO4)3 + 2 MnSO4 + K2SO4 + 8 H2O

 Procedure
1-Transfer 10 mL of Ferrous sulphate (sample) accurately into a clean conical flask.
2- then add 10 mL of Zimmerman reagent by measuring cylinder.

Titrant: 0.1 N KMnO4 (self indicator)

E.P : Colorless………First persistent pink.

 Note
 KMnO4 is the oxidizing agent, while; FeSO4 is the reducing agent.
10 FeSO4 + 2 KMnO4 + 8 H2SO4 5 Fe2(SO4)3 + 2 MnSO4 + K2SO4 + 8 H2O

Calculations:
E.P. × f × F × 𝟏𝟎𝟎𝟎
Concentration of (FeSO4) sample (gm / L) =
volume of sample (mL)

𝑀.𝑤𝑡 𝐹𝑒𝑆𝑂4 × 𝑁 𝐾𝑀𝑛𝑂4

𝐅 FeSO4 = = ………… gm FeSO4.
𝑛 𝐹𝑒𝑆𝑂4 × 1000

- The mass number are as follows: Fe = 55.845 g/moL, S = 32.00 g/moL, and O = 16.00 g/moL.

- n = 1, as Fe2+ is oxidized to Fe3+ , i.e. loss of 1 electron by one molecule.

 If the sample were FeCl2, Zimmermann – Reinhard reagent would be
added to the reaction media.

 Zimmerman reagent is: (MnSO4 + H2SO4 + H3PO4)

MnSO4: The abundant Mn2+ (MnSO4) added to the solution reduces the oxidizing potential of the permanganate
(MnO4-). Thus, permanganate is prevented from oxidizing the chloride ions. This is important for preventing the
overconsumption of the titrant and for accurate E.P.

2- H2SO4 (acidifying agent): to make the medium acidic enough to reduce MnO4- into Mn2+ not into MnO2
(Brown ppt).

3- H3PO4: the (Fe+3) solution is yellowish in color which may hinder the inspection of the first pink at E.P. So,
H3PO4 in Zimmerman tends to complex the resulting (Fe3+), leaving behind a colorless solution. Also,
decrease [Fe3+] & so lower E of (Fe3+/Fe2+) system to make it more easily oxidized by MnO4-
 Assignment
 In a laboratory experiment, a secondary standard solution of potassium permanganate (KMnO₄)
with a normality of 0.15 N was prepared into 250 mL volumetric flask.
 The prepared secondary standard solution was initially standardized against 15.00 mL of 0.15 N
oxalic acid, a recognized primary standard, to establish its accuracy. The E.P. of this standardization
process was determined to be 12.50 mL. Following this, the secondary standard was assessed for
potential deviations in concentration (either dilution or concentration).
 Subsequent to this adjustment, the secondary standard solution was re-standardized using the oxalic
acid as the primary standard, resulting in a revised E.P. of 14.4 mL.
 Finally, the adjusted secondary standard solution was utilized to titrate a 20.00 mL sample of
ferrous sulfate (FeSO₄), where the equivalence point was determined to be 19.1 mL.
 Questions:
A. Calculate the correction factor (f) for the secondary standard and determine whether it is acceptable or not
(diluted or concentrated). If it is not acceptable, explain how to adjust the remaining volume of the secondary
standard.
B. Calculate the new correction factor after re-standardization of 2ry standard.
C. Determine the concentration of the ferrous sulfate sample in g/L, given that the mass number are as follows: Fe
= 55.845 g/mol, S = 32.00 g/mol, and O = 16.00 g/mol.
D. After calculating the concentration in g/L, convert the result to g%, g/mL, Normality (N), and Molarity (M).
Assignment

1- What is the oxidation number of ?

nitrogen in nitric acid (HNO3), chromium in calcium dichromate (CaCr2O7), sulphur in

sulphuric acid (H2SO4), carbon in dichloromethane (CH2Cl2).

2- When K2Cr2O7 is converted to K2CrO4, the change in the oxidation number of

chromium is
a- 0 b- 2 c- 4 d- 6

3- In which of these two compounds (SO3 - CaS) does Sulphur have higher oxidation
number ?
Assignment

4- 10 FeSO4 + 2 KMnO4+ 8 H2SO4 5 Fe2(SO4)3 + 2 MnSO4 + K2SO4 + 8

H2O

[Given: Fe = 55.845 g/moL, S = 32.00 g/moL, O = 16.00 g/moL, K = 39 g/moL, and Mn

= 54.938].

According to the above equation :

A- The reductant (reducing agent) is ………. , and its equivalent weight is ……

B- The oxidant (oxidizing agent) is …………..., and its equivalent weight is ……

Thank you