PART 1
Outline
• Types of volumetric analysis
• Acid base titration
• Principle of acid base titration
• Term used (definition)
• Direct and back titration (involve calculation)
• pH and pOH
• Acid base titration Curve:
Strong acid and strong base
Strong acid and weak base
Strong base and weak acid
Weak acid weak base
Calculation of pH change during strong acid-strong
base titration
Acid base indicators, choice of indicators
Quantitative Classical Chemical
Analysis
Quantitative Classical Chemical Analysis
Gravimetry Volumetric
Acid-base Precipitation Complexometric Redox
Titrations
General term for method in quantitative chemical
analysis in which the amount of substance is
determined by the measurement of the volume that
the substance occupies.
Commonly used to determine the unknown
concentration of a known reactant.
Volumetric analysis is often referred to as TITRATION
INTRODUCTION TO TITRATION
TITRATION PRINCIPLE
• TITRATION is a process in which a standard reagent
of a known concentration from a buret (the
TITRANT) is added to a solution containing the
ANALYTE until the reaction between the analyte and
the reagent is judged to be complete.
• A general chemical reaction for titrimetric analysis is
aA + tT product
where a moles of analyte A contained in the sample reacts
with t moles of the titrant Tin the titrant solution.
THE PROCESS - PREPARATION
Two solutions are used:
The solution of unknown concentration.
The solution of known concentration which is also known
as the standard solution.
Write a balanced equation for the reaction
between two chemicals.
Clean all glassware to be used with distilled
water. The pipettes and burettes will be
rinsed with the solutions to be measured.
TITRATION SET UP
Burette-attached to a clamp stand above a
conical flask.
Burette is filled yellow standard solution.
A pipette is used to measure an aliquot of other
solution (purple:unknown concentration) into
conical flask.
Indicator is added to the conical flask.
Read the initial level of liquid in burette
Turn the tap to start titrate. Swirl the flask
continuously. When the indicator begins to
change colour slow the flow.
When the colour changes permanently, stop
[Link] the final volume.
This volume is called a TITRE.
Repeat the titration with a new flask now that
you know the ‘rough’ volume required.
Repeat until get precise results.
TERMS USED in
Volumetric Analysis
♪ Titration
♪ Titrant
♪ Analyte
♪ Indicator
♪ Equivalence Point vs End Point
♪ Titration Error
♪ Direct Vs Back Titration
♪ Blank Titration
Titration
A process in which a standard reagent is added
to a solution of analyte until the reaction between
the two is judged complete
• Titrant solution is volumetrically delivered to the
reaction flask using a burette.
• Delivery of the titrant is called a Titration
• An indicator is often added to the reaction flask to
signal when all of the analyte has reacted.
• Analyte: species to be determined
DEFINITION OF TERMS
• The equivalence point: the point at which
an equivalent or stoichiometric amount
(mol) of added standard reagent is
equivalent to the amount (mol) of analyte
• based on the stoichiometric equation.
• The end point: the point in a titration at
which the indicator changes colour.
The point at which the reaction is observed to be completed is the end
point.
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 VS
EQUIVALENCE POINT
END POINT EQUIVALENCE POINT
The point at which an equivalent or
The point at which the reaction is
stoichiometric amount of titrant is
observed to be completed
added to the analyte
The end point signal frequently occurs at
some point other than the equivalence The point at which the reaction is
point which tells the analyst to stop complete
adding TITRANT and record the volume.
Theoretically at the equivalence
point we can calculate the amount
The selected indicator should change
of titrant that is required to react
color very near to the equivalent point.
EXACTLY with the amount of
analyte present.
• BLANK TITRATION:
• titration of a solution that contains all the reagents
except the ANALYTE
• DIRECT TITRATION: A direct addition of standard
titrant TO the analyte in the presence of acid-base
until the reaction is complete and reaching the end
point (colour change of the indicator)
• BACK TITRATION: In this titration the excess of
a standard solution used to consume the analyte is
determined by the titration with a second
standard solution.
SUCCESSFUL VOLUMETRIC
TITRATION …..
Reaction must be stoichiometric, well defined
reaction between titrant and analyte.
Reaction should be rapid.
Reaction should have no side reaction, no
interference from other foreign substances.
Must have some indication of end of reaction,
such as color change, sudden increase in pH or
zero conductivity
Known relationship between endpoint and
equivalence point.
5.1
TYPES OF
VOLUMETRIC ANALYSIS
(i) ACID-BASE
(ii) PRECIPITATION
(iii) COMPLEXOMETRIC
(iv) REDOX(REDUCTION-OXIDATION)
TYPES OF TITRATION
When the reaction involves an acid and a base,
the method is referred to as an acid-base
titration.
When the reaction involves oxidation and
reduction, the method is referred to as a
redox titration.
Titrations Examples
Acid-base Determination of % of acetic
acid in vinegar
Complexometric Water Hardness
(determination of
Calcium and
magnesium )
Precipitation Determination of chloride
(Cl-) in water
Redox Quantification of hydrogen
peroxide (H2O2)
5.2 ACID-BASE TITRATION
Titrations involving acid-base neutralization reactions.
Many compounds, both organic and inorganic are
either acids or bases, and can be titrated with
standard solution of a strong base or a strong acid.
Involves a neutralization reaction in which an acid is
reacted with an equivalent amount of base
Titration curve - pH of the solution versus volume of
titrant added
Titrant - usually strong standard acid or strong base
Equivalence point - is the point of stoichiometric
equivalence between the analyte and the reagent
End point - a point when reaction is completed
What happened
during Titration
DIRECT TITRATION
analyte + titrant product
unknown known
Example: Quantification of acetic acid in vinegar
CH3COOH + NaOH → CH3COONa+ H2O
A direct addition of standard titrant TO the
analyte in the presence of acid-base until the
reaction is complete and reaching the end point
DIRECT TITRATION (ACID-BASE)
EXAMPLE 1
A 0.2638 g soda ash is analyzed by titrating the
sodium carbonate with the standard 0.1288 M HCl
solution, requiring 38.27 mL. The reaction is :
Na2CO3 + 2HCl CO2 + H2O + 2NaCl
Calculate the percent of sodium carbonate (w/w)
the [Link]
DIRECT TITRATION (ACID-BASE)
Solution:
- Mole of HCl = 38.27 x 10-3 Lx 0.1288 = 4.929 x 10-3
- Mole of Na2CO3 = ½x 4.929 x 10-3 = 2.465 x 10-3
- Mass of Na2CO3 = 2.465 x 10-3 mol x 105.99 g/mol =
0.2612 g
- % Na2CO3= mass Na2CO3 X 100
mass sample
= 0.2612 g X 100 = 99.02 % (w/w)
0.2638 g
DIRECT TITRATION (ACID-BASE)
EXAMPLE 2
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 g/mol.
H2A + 2NaOH 2H2O + Na2A
[Link] whether the equivalence point is greater or less
than 7. (greater than 7)
[Link] a suitable indicator that can be used in the
above titration. (phenolphtalein)
[Link] the MOLARITY of the base.
0.316 M
DIRECT TITRATION (ACID-BASE)
EXAMPLE 3
Calculate the concentration of vinegar in % (w/v) for a
titration of 25 ml of vinegar which was primarily diluted
10 times (25mL into 250mL), reacted with 22.4 mL of 0.1
M NaOH standard solution.
CH3COOH + NaOH → CH3COONa + H2O
[Link] concentration of Vinegar in % (w/v)
5.38 %
SELF-EXERCISE
1. 50mL of 0.2mol L-1 NaOH neutralised 20mL of H2SO4.
Determine the concentration of the acid (0.25 M)
2. 25.0mL of 0.05M Ba(OH)2 neutralised 40.0mL of nitric acid.
Determine the concentration of the acid. (0.0625 M)
BACK – TITRATION
• The excess of a standard solution used to consume the
analyte is determined by the titration with a second
standard solution.
• Is applied to analysis involving reactions that are slow to
go to completion and a sharp end point cannot be
obtained.
• Mol(excess)= initial mole(total) – mole reacted or
• Mol (reacted) = initial mole(total) – mole excess
BACK TITRATION
EXAMPLE 1
• 1.125 g Ca(OH)2 sample was dissolved in 100 mL 0.25
M HCl. The excess acid is back titrated with 0.05 M
Na2CO3 standard solution and it required 20.25 mL to
reach the end point. Calculated % (w/w) purity of
Ca(OH)2.
Reaction:
Ca(OH)2 + 2HCl CaCl2 + 2H2O
2HCl + Na2CO3 2NaCl + CO2 +H2O
REMEMBER:
Ca(OH)2 + 2HCl CaCl2 + 2H2O (1)
Equation 1 : Mole reacted
2HCl + Na2CO3 2NaCl + CO2 +H2O (2)
Equation 2 : Always excess (mole excess)
Initial mole always given in question
Solution:
Or mol: 0.05 M x (20.25 x 10-3 L)
Mol of Na2CO3 = MV = 0.05 Mx 20.25mL
1000 1000
= 1.0125 x 10-3 mol
Mol of HCl (excess) = 2 mol HCl x 1.0125 x 10-3 mol Na2CO3
1 mol Na2CO3
= 0.00202 mol HCl
Initial mol of HCltotal = 100 x 10-3L x 0.25 M
(given in question) = 0.025 mol
Mol HCl reacted with Ca (OH)2:
{Mol (excess) = initial mole/total – mole reacted }
mole reacted = initial mole – mole excess
Mol HCl reacted =(0.025 – 0.00202) mol
= 0.02298 mol HCl
(compare from Eq 1)
(mol Ca(OH)2
Mol of Ca(OH)2 = ½ x 0.02298 mol HCl
(mol HCl)
= 0.01149 mol
Mass Ca(OH)2 = 0.01149 mol x 74 g/mol = 0.85 g
% Ca(OH)2 = mass Ca(OH)2 (reacted) X 100
mass Ca(OH)2 (sample)
= 0.85 g x 100
1.125 g
= 75.56 % (w/w)
BACK TITRATION
EXAMPLE 2
150.0 mL of 0.2105 M nitric acid was added in
excess to 1.3415 g calcium carbonate. The excess
acid was back titrated with 0.1055 M sodium
hydroxide. It required 75.5 mL of the base to
reach the end point.
Calculate the percentage (w/w) of calcium
carbonate in the sample.
First write a balance equation for the above
reactions.
2HNO3 + CaCO3 Ca(NO3)2 + CO2 + H2O ------ 1
HNO3 + NaOH NaNO3 + H2O ------- 2
From Equations above:
2 mole HNO3 required 1 mole CaCO3
1 mole HNO3 required 1 mole NaOH
Initial mole of acid (total) = Molarity x volume (L)
= 0.2105 mol/L x 0.150 L
= 0.031575 mol
Remaining/excess acid during back titration.
Mole of excess acid
= molarity x volume (L)
= 0.1055 mol/L x 0.0755 L
= 0.007965 mol acid.
Mole of acid reacted with CaCO3
= Initial – remaining/excess
= ( 0.031575 – 0.007.965 ) mol
= 0.02361 mol
Mole of CaCO3 in sample= ½ x mmole acid
= ½ x 0.02361
= 0.011805 mol
Mass of CaCO3 in sample = mole x molar mass
= 0.011805 mol x 100 g/mol
= 1.1805 g.
% (w/w) of CaCO3 in sample
weight CaCO3
x100 %
weight of sample
1.1805
x100 %
1.3415
= 87.99 % (w/w)
EXAMPLE 3
• The sulfur content of 0.003 g steel sample is
determined by converting it to H2S gas. The gas
is then dissolved in 10.00 mL 0.0050 M I2
solution. The excess I2 is then back titrated with
0.002 M Na2S2O3 solution. 5.60 mL of the
thiosulfate solution is required to reach the end
point. Calculate % (w/w) sulfur in the steel
sample. The reactions involved:
H2S + I2 S + 2I- + 2H+ …….equation 1
I2 + 2 S2O32- 2I- + S4O62- ………equation 2
• (ans: 1.421 mg)
Solution
• Initial mole of I2 = 10 x 0.0050 = 5 x 10-5 (given in question)
1000
mole Na2S2O3 = 5.6 x 0.002 = 1.12 x 10-5
1000
• Mole of I2 (excess) = ½ (1.12 x 10-5) = 5.6 x 10-6 (Eq 2)
Mole of I2 that reacted with Na2SO3 = initial mole – mole (excess)
= 5 x 10-5 – 5.6 x 10-6
= 4.44 x 10-5
• From equation 1 (H2S + I2 S + 2I- + 2H+)
mol S = 4.44 x 10-5
mass S = 4.44 x 10-5 x 32 = 1.42 x 10-3 g or 1.42 mg
%S = mass S(reacted) X 100
mass steel(sample)
= 1.42 x 10-3 g x 100
3.0 x 10-3 g
= 47.33 % (w/w)
EXAMPLE 4 ANALYSIS OF ASPIRIN
(BACK TITRATION)
Aspirin: active ingredient in aspirin:
acetylsalicylic acid. Find:
1)Aspirin is hydrolyzed to acetic acid and Total mole of NaOH = (give in question)
salicylic acid byreaction with excess Mole of NaOH (excess) = ?
Mole of NaOH that reacted with acethylsalicyclic acid = ?
NaOH. Mol total – mol excess)
Mole of acethylsalicyclic acid =? (compare eq)
Mass of acethylsalicyclic acid = ?
% w/w = mass of acethylsalicyclic acid x 100%
mass of aspirin
2NaOH +CH3COO-C6H4-COOH
CH3COONa + HO-C6H4-COONa + H2O
Equation 1 : Mole consumed
(2) Excess NaOH is titrated with HCl
NaOH + HCl NaCl + H2O
Equation 2 : Always excess (mole excess)
pH & pOH CALCULATION
pH
Defining equation for pH
pH log[H ]
[H ] anti log(pH) 10pH
TIPS where p = - log
The higher the pH, the less acidic the solution
The lower the pH, the more acidic the solution
Figure
32
pOH
Defining equation for pOH
pOH log[OH ]
[OH ] antilog[pOH] 10pOH
TIPS where p = -log
The higher the pOH, the more acidic the solution (eg if
pOH
= 12, pH = 14-12 = 2, pOH = 13, pH = 14-13 = 1)
The lower the pOH, the more basic the solution
(eg if pOH = 5, pH = 14-5 = 9, pOH = 4, pH =
14-4 = 10)
- [H3O+] > 1.0 x 10-7 M -- pH < 7 solution is acidic
- [H3O+] < 1.0 x 10-7 M -- pH > 7 solution is basic
pH = - log [H3O+] or – log [H+]
pOH = - log [OH-]
pH + pOH = 14 = pKw, pKw = -log Kw = 14
[H+][OH-] = Kw =1.0 x 10-14
Example
1. Calculate the pH, pOH, [H+] and [OH-] of a 0.20 M H2SO4 solution
H2SO4 2 H+ + SO42-
(0.2) 2 (0.2)
TIPS
= 0.4
(a) [H+] = 0.4
(b) pH =-log (0.4) = 0.398
pH +pOH = 14
(c) pOH = 14 – pH
= 14 – 0.398 = 13.602 [H+][OH-] = 1 x 10-14
[OH-] = 1 x 10-14
or 0.4
(d) [OH-]= 10- pOH = 2.5 x 10-14
= 10-13.602 = 2.5 x 10-14
42
2. Calculate the pH, pOH, [H+] and [OH-] of a 0.20 M Ba(OH)2 solution
Ba(OH)2 Ba2+ + 2 OH-
(0.2) 2 (0.2)
TIPS
= 0.4
(a) [OH-] = 0.4
(b) pOH =- log (0.4) = 0.398
pH +pOH = 14
(c) pH = 14 – pOH
= 14 – 0.398 = 13.602 [H+][OH-] = 1 x 10-14
[H+] = 1 x 10-14
or 0.4
(d) [H+]= 10- pH = 2.5 x 10-14
= 10-13.602 = 2.5 x 10-14
43
3. What is the pH of 0.050 M HNO3?
HNO3 H+ + NO3 -
0.05
pH = -log[H+] pH = -log[0.050] =1.3
4. Calculate the pH of 0.03 M HCl
HCl H+ + Cl
0.03 0.03
pH = -log[H+] pH = -log[0.03] =???
5. What is the pH of a solution prepared by dissolving 1.00 g
of Ba(OH )2 per liter?
Molarity of Ba(OH )2 = 1.00g/171g/mol = 5.85 x 10-3 M
1L
Ba(OH )2 Ba 2+ + 2OH-
2(5.85 x 10-3 )
pOH= - log [OH], pOH = -log (2x 5.85 x 10-3 ) = 1.93
pH = 14 –pOH = 14- 1.93 = 12.1
[Link] the [H+] for a solution
having pH= 3.2
pH = -log [H+]
[H+] = 10-pH
=10 -3.2 = 6.3 x 10-4
TRY!
Calculate the pH and pOH of a 1.00 x 10-3 M
solution of acetic acid.
(answer: pH=3.88;pOH=10.12)
