TOPIC 4: VOLUMETRIC
ANALYSIS (BACK TITRATION)
Assoc. Prof. Dr. Sabiha Hanim Saleh
Faculty of Applied Sciences
UiTM Shah Alam
May2021
VOLUMETRIC/TITRIMETRIC ANALYSIS
◦ ACID –BASE TITRATION
◦ BACK TITRATION
◦ COMPLEXOMETRIC TITRATION
◦ PRECIPITATION TITRATION
◦ REDOX TITRATION
BACK TITRATION
A back titration is a titration method where the
concentration of an analyte is determined by
reacting it with a known amount of excess reagent.
The remaining excess reagent is then titrated with
another, second reagent.
Direct
titration
In a direct titration, a standard titrant is
added to the analyte until reach the end
point.
In a back titration, a known excess of
Back
titration standard reagent is added to the solution,
and the excess is titrated.
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 colour 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 (Aspirin tablets comprise of acetylsalicylic
acid) with NaOH is not practical because the reaction is slow.
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
The final titration to the equivalence point is called a BACK TITRATION
Exercise 1
A 0.1504 g of impure sample containing magnesium carbonate was
dissolved in 50.00 mL of 0.1140 M hydrochloric acid, then boiled to
eliminate carbon dioxide. Back-titration of the excess acid required
24.21 mL of 0.09802 M NaOH. Determine the percentage of
magnesium carbonate in the sample. (Mg=24.32, C=12.01, O=16.00)
Initial mol HCl = (50/1000) L x 0.1140 mol/L
= 5.7 x 10-3 mole.
HCl + NaOH → NaCl + H2O
Mole NaOH used to react with HCl = (24.21/1000) x 0.09802 mol/L
= 2.373 x 10-3 mole
= 2.373 x 10-3 mole
Therefore, amount HCl reacted with carbonates
= initial mol HCl - mol HCl react with HCl
= ( 5.7 - 2.373) x 10-3 mole = 3.327 x 10-3 mole.
2HCl + MgCO3 → MgCl2 + H2O + CO2
From the equation : 2 moles HCl reacted with 1 mole MgCO3
Therefore 3.327 x 10-3 mole react with : = (3.327 x 10-3 / 2 ) mole x 1
=1.6635 x 10-3 mole MgCO3
Mass MgCO3 in sample = 1.6635 x 10-3 x 84.33g/mol
= 0.1403 g
% MgCO3 in sample = 0.1403/0.1504 x 100 = 93.28% (w/w)
Exercise 2
The concentration of ethyl acetate (CH3COOC2H5) in a sample was determined by
diluting 10 mL sample to 100 mL. A volume of 20.0 mL of this diluted solution
was refluxed with 45.00 mL of 0.0250 M KOH solution. The reaction is as
follows:
CH3COOC2H5 + OH- ↔ CH3COO- + C2H5OH
After cooling, the excess OH- was back titrated with 3.50 mL of 0.050 M H2SO4
solution. Calculate the weight of ethyl acetate per 100 mL in the initial sample.
(H=1.008, C= 12.01, O= 16.00)
CH3COOC2H5 + OH- ↔ CH3COO- + C2H5OH …….(1)
2KOH + H2SO4 → K2SO4 + 2H2O ……… (2)
initial mol KOH = 0.025 x (45/1000) = 1.125 x 10-3 mol
mol H2SO4 react with KOH = 0.05 x (3.5/1000 ) =1.75 x 10-4 mol
From the equation 2 :
2 mol KOH = 1 mol H2SO4
Amount of KOH excess = 2 x 1.75 x 10-4 = 3.5 x 10-4 mol
mol KOH reacted with ethyl acetate = (1.125 x 10-3 - 3.5 x 10-4 )
= 7.75 x 10-4 mol .
From equation 1: 1 mol CH3COOC2H5 = 1 mol KOH
Therefore, mol CH3COOC2H5 = 7.75 x 10-4 mol .
Molarity of CH3COOC2H5 =( 7.75 x 10-4 mol / 20 x 10-3)
=0.0388 M (diluted solution)
Mol of CH3COOC2H5 in 100 mL initial sample = 0.0388 x (100/1000)
= 0.0039 mol
Mass of CH3COOC2H5 = 0.0039 g x 88.10 g/mol
= 0.3436 g.
Exercise 3
A K2CO3 solution was prepared by dissolving 0.6500 g K2CO3 in sufficient water
to produce 250.00 mL solution. A 20.00 mL aliquot is taken and put into an
Erlenmeyer flask. A 20.00 mL of 0.1700 M HCl is added into the flask. The
resulting solution is then titrated with 0.12 M NaOH. Calculate the volume of
NaOH required for the back titration. (K=39.10, C= 12.01, O=16.00)
K2CO3 (aq) + 2HCl 2KCl(aq) + H2O(l) + CO2(g)
NaOH (aq) + HCl NaCl(aq) + H2O(l)
Initial mol HCl = (20 x 0.1700)/1000 = 3.4 x 10−3 mol
0.6500 𝑔
Mol 𝐾2 𝐶𝑂3 = = 4.703 x 10−3 mol in 250 mL
138.21 𝑔/𝑚𝑜𝑙
Mol 𝐾2 𝐶𝑂3 in 20 mL,
20 𝑚𝑙
x 4.703 x 10−3 = 3.762 x 10−4
250 𝑚𝑙
Refer to 1st chem. Eq.
𝑚𝑜𝑙 𝐻𝐶𝑙 2
=
𝑚𝑜𝑙 𝐾2 𝐶𝑂3 1
Mol HCl react with 𝐾2 𝐶𝑂3 = 2 x 3.762 x 10−4 = 7.525 x 10−4 𝑚𝑜𝑙
Mol HCl excess (remaining) = initial mol HCl – mol HCl reacted with 𝐾2 𝐶𝑂3
= (3.4 x 10−3 - 7.525 x 10−4 ) = 2.648 x 10−3
Refer to 2nd chem. Eq.
Mol NaOH : mol HCl = 1: 1
So, mol NaOH = 2.648 x 10−3
Molarity = mol/V = 0.12
(2.648 x 10−3 ) / V = 0.12
V = (2.648 x 10−3 )/0.12 x 1000 = 22.1 mL
