CHAPTER 5

TITRIMETRIC METHODS OF ANALYSIS

1
 OVERVIEW OF TITRIMETRY

• Definition:
Titrations (or titrimetric method) are based on
measuring the amount of a reagent of known
concentration that reacts with the unknown.
It is the process of determining unknown
concentration by adding the small increments of
standard solution until the reaction is just
complete.
A general equation can be expressed:
aA + tT → products
where, A: analyte; T: titrant
2
OVERVIEW OF TITRIMETRY
• Keywords of Titration
Equivalence point: The point (e.g., volume of titrant)
in a titration where (theoretically) stoichiometrically
equivalent amounts of analyte and titrant react.
Indicator: A colored compound whose change in
color signals the (experimental) end point of a
titration.
End point: The point (e.g., volume of titrant) in a
(experimental) titration where we stop adding titrant
in an experiment.
Titration error: The determinate error in a titration
due to the difference between the end point and the
equivalence point.
3
 OVERVIEW OF TITRIMETRY
• Type of Titrations based on Chemical Reactions:
i.Acid-Base Titrations:
H+ + OH– → H2O K= 1/Kw
ii.Precipitation Titrations:
Ag+(aq) + Cl–(aq) → AgCl(s) K=1/Ksp
iii. Redox Titrations:
5 H2O2 + 2 MnO4– + H+ → 5 O2 + 2 Mn2+ + 8H2O
iv.Complexometric Titrations:
EDTA + Ca2+ → (Ca–EDTA)2+

4
 OVERVIEW OF TITRIMETRY
• Type of Titrations based on Measuring Techniques:
i.Volumetric titrimetry: Measuring the volume of a
solution of a known concentration (e.g., mol/L) that
is needed to react completely with the analyte.
ii.Gravimetric (weight) titrimetry: Measuring the
mass of a solution of a known concentration (e.g.,
mol/kg) that is needed to react completely with the
analyte.
iii.Coulometric titrimetry: Measuring total charge
(current x time) to complete the redox reaction, then
estimating analyte concentration by the moles of
electron transferred.
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 OVERVIEW OF TITRIMETRY
• Type of Titration Curves:

6
 GRADES OF CHEMICALS
• Terms and Definitions:
i.Reagent Grade:
The reagents which meets or surpasses the latest
American Chemical Society specifications.
ii.Primary standard:
The reagent which is ready to be weighted and
used prepare a solution with known concentration
(standard).
Requirements of primary reagent are:
- Known stoichiometric composition
- High purity - Nonhygroscopic
- Chemically stable both in solid & solution
- High MW or FW
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GRADES OF CHEMICALS

• Secondary standard:
A standard which is standardized against a
primary standard.
• Certified reference materials (CRM):
A reference material, accompanied by a
certificate, which has been analysed by different
laboratories to determine consensus levels of the
analyte concentration.

8
 GRADES OF CHEMICALS

• NIST Standard Reference Material® (SRM):

A CRM issued by NIST that also meets additional
NIST-specific certification criteria and is issued with
a certificate.
• Standardization:
The process by which the concentration of a
reagent is determined by reaction with a known
quantity of a second reagent.

9
 TITRATION CALCULATIONS

• Terms and Definitions:

Blank Titration: Titration procedure is carried
out without analyte (e.g., a distilled water
sample). It is used to correct titration error.
Back titration: A titration in which a (known)
excess reagent is added to a solution to react
with the analyte. The excess reagent
remaining after its reaction with the analyte, is
determined by a titration.
10
Titrimetric methods include a large and
powerful group of quantitative procedures
based on measuring the amount of a reagent
of known concentration (standard solution-
titrant) that is consumed by the analyte.
Titrimetry is a term which includes a group of
analytical methods based on determining the
quantity of a reagent of known concentration
that is required to react completely with the
.analyte
Basic principle

aA +bB → Products

A: Titrant (standard solution)

B: Analyte (unknown )
a and b are number of moles of each
Requirments inTitration

stoichiometric reaction -1
rapid rate reaction -2
quantitative reaction (99.9%complete at -3
stoichiometry)
have a defined end or equivalence point-4
 Standard solutions
Standard Solution
- A primary standard
- A secondary standard
Standardization
A process in which concentration of a volumetric
solution is determined by titrating it with a known
mass of a primary standard.
 Titration: This is
performed by adding a Solution
Solution
of NaOH
of NaOH

standard solution from a

buret or other liquid-
dispensing device to a
solution of the analyte Solution

until the point at which the of HCl

reaction is believed to be 5 mL

complete.

15
PRIMARY STANDARD

• HIGH PURITY
• ATMOSPHERIC STABILITY
• INDEPENDENT OF HUMIDITY
• MODEST COST
• LARGE MOLAR MASS
• NON HYROSCOPIC

16
Calculations with Molarity
The mole: is the formula weight of a substance
expressed in grams

Number of moles = weight in Grams/formula weight

Number of m.moles = weight in milligrams/formula

weight

Molarity= Moles/Liter or mmoles/ml

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Moles= Volume (L) . (M)
Weight (g) = Volume (L) . (M) . formula weight (g)

m.Moles= Volume (mL) . (M)

Weight (mg) = Volume (ml) . (M) . formula weight (g)

18
 Calculating the results of Titration
Needs: the volume and molarity of the titrant
aA + bB → Products
)analyte or substance titrated( )Titrant(

No. of m.moles of A = Volume of A titrated (mL) . Molarity of A

(M)

Or mmolesA = mLA . (MA)

No. of m.moles of B is obtained by multiplying the No.
of mmoles of A by the combining ratio (b/a)

19
mmolesB = mmolesA . (b/a) = mlA . (MA). (b/a)

20
If the weight of substance is needed: from no.
of mmoles
Wt (mg) = mmoles . Formula wt (g)

mgB = (mlA) . (MA). (b/a) . (formula WtB)

If % of B is needed in a sample = (Wt B/Wtsample).100

The same is B% =(mgB/mgS).100
B% = (mlA) . (MA). (b/a) . (form WtB)(100)/mgS

21
22
Calculating the molarity of a solution from a standardizing
titration
This means that from the weight of primary standard substance
(B )when dissolved and titrated with other solution, the molarity
:of the solution (A) can be calculated as follows

aA + bB → Products
)primary standard( )SolutionA(

(mlA) (MA)/a = (mlB) (MB)/b

(mlB) (MB) = mmolesB = mgB /Form WtB

(MA) = (a/b)mgB/ (mlA) (Form WtB) 23

24
Exercises
Excercize1

How many ml of 0.25 M NaOH will react with 10.0 ml of 0.10 M H2SO4.

25
 Solution:

H2SO4 + 2 NaOH  Na2SO4 + 2 H2O

mmol NaOH = 2 mmol H2SO4

(½) x MNaOH x VmL(NaOH) = M(H2SO4) x VmL(H2SO4)

0.25 x VmL = 2 x 0.10 x 10

VmL = 8 ml

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:Exercise2

g sample containing NaHCO3 (FW = 0.4671

84.01 mg/mmol) was dissolved and titrated with
0.1067 M HCl requiring 40.72 mL. Find the
.percentage of sodium bicarbonate in the sample

27
Solution

write the equation in order to identify the stoichiometry

NaHCO3 + HCl → NaCl + H2CO3

Now it is clear that the number of mmol of sodium bicarbonate

is equal to the number of mmol HCl from the equation:
M1.V1 (HCl)=M2.V2 (NaHCO3)
mmol NaHCO3 = mmol HCl
mmol = M x VmL
mmol NaHCO3 = (0.1067 mmol/ml ) x 40.72 mL = 4.345 mmol
Now get mg bicarbonate by multiplying mmol times FW

mg NaHCO3 = 4.345 mmol x (84.01 mg/mmol) = 365.01mg

% NaHCO3 = (365.01 x 10-3 g/0.4671 g) x 100 = 78.14% 28

 Exercize3
A 0.1876 g of pure sodium carbonate (FW = 106
mg/mmol) was titrated with approximately 0.1 M HCl
requiring 35.86 ml. Find the molarity of HCl.

Solution

The first thing writing the equation of the reaction.

Na2CO3 + 2 HCl  2 NaCl + H2CO3

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 from the equation
2 mmol HCl react with 1 mmol carbonate
mmol HCl = 2 mmol Na2CO3 or

MHCl X Vml 1/2 = mmol Na2CO3

substitute for mmol carbonate by mg carbonate/FW

carbonate. This gives
MHCl x 35.86 = 2 x 187.6 mg/ (106 mg/mmol)

MHCl = 0.09872 M

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 Back-Titrations
In back titration an accurately known amount of a
reagent is added to analyte in such a way that some
excess of the added reagent is left. This excess is then
titrated to determine its amount.
• aA + bB → Products + A(excess)
• (Titrant1) (analyte)

• Then back titration of A(excess) with Titrant2 C

• cC + dA → Products
• (Back titration) (excess)
• Titrant2
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mmol reagent(Titrant1) taken = mmol reagent(net)
reacted with analyte + mmol reagent(excess) titrated
with Titrant2

then the analyte can be determined since

mmol reagent added are known, and mmol
reagent titrated can be calculated from back
.titration

A added = A net + A excess

mmol reagent taken = mmol reagent net reacted + mmol reagent back titrated

mmol reagent net reacted = mmol reagent taken – mmol reagent back titrated
32
Finally, the number of mmol reagent net reacted
with analyte can be related to the number of
mmol analyte from the stoichiometry of the
reaction between the two substances as normal
titration up on the equation.
aA + bB → Products

33
 . Now net calculations will be as follows:

• aA + bB → Products + A(excess)
• (Titrant1) (analyte)

• cC + dA → Products (Back titration)

Titrant2 (excess)

Net reacted

Net reacted

34
Importance of back titration:

Back-titrations are important especially in some situations like:

1. When the rate of reaction is slow.

2. When the titration reaction doesn't have a good end point.

35
:Example

36
:Example

37
Exercise

0.1195 g of Na2CO3 was mixed in 30 mL of

boiled water. Next, 40 mL of HCl solution was
added turning the solution colorless to indicate
the presence of excess acid. It then required
17.51 ml of .1096 M NaOH to back titrate the
excess hydrogen ion in solution to faint pink
phenolphthalein endpoint. Calculate the
concentration of the unknown HCl solution.

38
First work out how many excess moles of HCl
that were neutralized by the NaOH

HCl + NaOH -----------> NaCl + H2O

1 mole HCl needs 1 mole NaOH to be

neutralized, a 1:1 ratio
So moles HCl neutralized = moles NaOH added
moles NaOH = Molarity x Litres
= 0.1096 M x 0.01751 L
= 0.001919096 moles HCl were in excess.
39
Then we need moles HCl needed to react all
the Na2CO3

Na2CO3 + 2HCl ------------> 2NaCl + CO2 + H2O

1 mole Na2CO3 needs 2 moles HCl in order to

fully react.
moles Na2CO3 = Wt / FWt
= 0.1195 g / 105.9884 g/mol
= 0.00112748 moles Na2CO3
So moles HCl used up by Na2CO3 = 2 x moles
Na2CO3 40
total moles HCl in solution =
0.00225496 + 0.001919096
moles HCl 0.004174 =

Molarity = moles / L

L 0.040 / 0.004174 =

M HCl 0.10435 =

41
:Calculations with Normality
The mole: is the formula weight of a substance
expressed in grams
The Normal or equivalent: is equivalent weight of a
substance expressed in grams
Normality (N) = Number of equivalents per liter
eq/liters or meq/ml =
Number of equivalents = weight in Grams/equivalent weight

42
Equivalents = Volume (L) . (N)
Weight (g) = Volume (L) . (N) . eq. weight (g)

m.eq= Volume (ml) . (N)

Weight (mg) = Volume (ml) . (N) .eq. weight (g)

43
Calculating the results of Titration
Needs: the volume and Normality of the
titrant
aA + bB → Products
)substance titrated( )Titrant(

Using Normality in calculations of titrations, never mind a

equal b or not, at equivalence in titrations:

No. of eq. of A = No. of eq. of B

NA . V A = N B . V B
44
No. of meq. of A = No. of meq. of B
NA . mlA = NB . mlB

45
How to calculate the equivalent weight:
The definition of an equivalent in terms of molarity
depends on the reaction a substance undergoes.
1- In acid base-reactions, one equivalent is the
number of grams of a substance that supplies or
combines with a hydrogen atom.
2- In oxidation-reduction, one equivalent is the
number of grams of a substance that supplies or
combines with an electron.
3- In complex formation, one equivalent is the number
of grams of a substance that supplies or react with
one ion.
46
Examples:
1eq of HCl = 1 mole = 35.5g of HCl
1eq of H2SO4 = 1/2 mole = 98/2 = 49g of H2SO4
1 eq of Fe2+ = 1mole (Fe2+ → Fe3+ + e) = 55.85g
1eq of KMnO4 = 1/5 mole, (KMnO4 + 5e+ ..→ Mn2+ +…)
31.6g =158.04/5 =
Its seen that the equivalent weight of a substance is related to its
:formula weight
eq Wt of HCl = form Wt / 1=35.5/1=35.5 g/eq
eq Wt of H2SO4= form Wt/2=98/2=49 g/eq
eq Wt of Fe2+=form Wt/1= 55.85/1=55.85 g/eq
eq of KMnO4 =158.04/5=31.6 g/eq 47
Now we can compute generalrules for calculating the
:equivalent Wt from the molecular Wt
in acid base reactions or substances: eq Wt= form -1
Wt/number of H+ replaced or denoted: i.e
H2SO4→2H+ + SO42-, eq Wt of H2SO4= form Wt/=98/2=49 g/eq
H3PO4→ 3H+ + PO43-, eq Wt of H3PO4 = 98/3=32.67 g/eq

48
:Precipitate-formation and complex formation titrations -2
eq. Wt of a metal ion= form Wt/chagre on the ion
Eq Wt of an anion = form Wt/no of metal-ion equivalents it
.reacts with
:Examples

49
Redox Reactions: eq Wt = form Wt/number of electrons -3
.gained or lost in the reaction
i.e

50
Examples and exercises:

HCl was standardized with 0.095 N solution of NaOH. If 25 -1

ml of HCl required 32.2 ml of NaOH solution. What is the
.concentration of HCl

51
2- A 200 g sample of a metal alloy is dissolved and then the
Tin is reduced to Tin (II). Titration of the Tin (II) required 22.20
ml of o.1 N K2Cr2O7.

Calculate the percentage of Tin in the alloy.

52
A 1.0 g sample required 28.16 ml of 0.1 N NaOH for -3
.titration to a phenolphthalein-indicator
Calculate the percentage of phosphoric acid (H3PO4) in the
.sample

53
4- A150 mg sample of pure Na2CO3 requires 30.06 ml of HCl
solution for titration:
2H+ + CO32- → CO2 (g) + H2O
2HCl + Na2CO3 → CO2 (g) + H2O+ 2NaCl

Calculate the normality of HCl.

54
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60
Features of the Strong Acid-Strong Base
Titration Curve

1. The pH starts out low, reflecting the high [H3O+] of the

strong acid and increases gradually as acid is neutralized
by the added base.
2. Suddenly the pH rises steeply. This occurs in the
immediate vicinity of the equivalence point. For this type
of titration the pH is 7.0 at the equivalence point.
3. Beyond this steep portion, the pH increases slowly as more
base is added.
 Sample Calculation: Strong Acid-Strong
Base Titration Curve
Problem 24-1. Consider the titration of 40.0 mL of 0.100 M
HCl with 0.100 M NaOH.
Region 1. Before the equivalence point, after adding 20.0 mL of
0.100 M NaOH. (Half way to the equivalence point.)
Amount moles of H3O+ remaining = Initial moles of H3O+
- Moles of OH- added

 amount (mol) of H O remaining
[H 3O ]  3
original volume of acid  volume of added base
 Sample Calculation: Strong Acid-Strong
Base Titration Curve (Cont. I)
Region 2. At the equivalence point, after adding 40.0 mL of 0.100
M NaOH.
Initial moles of H3O+ = 0.0400 L x 0.100 M = 0.00400 M H3O+
- Moles of OH- added = 0.0400 L x 0.100 M =0.00400 mol OH-
 Sample Calculation: Strong Acid-Strong
Base Titration Curve (cont. II)
Region 3. After the equivalence point, after adding 50.0 mL of 0.100
M NaOH. (Now calculate excess OH-)
Total moles of OH- = 0.0500 L x 0.100 M = 0.00500 mol OH- -
Moles of H3O+ consumed = 0.0400 L x 0.100 M =0.00400 mol

 amount (mol) of OH remaining
[OH ] 
original volume of acid  volume of added base
66
Titration of a Strong Acid with a
Strong Base
From the start of the titration
to near the equivalence point,
the pH goes up slowly.

67
Titration of a Strong Acid with a
Strong Base
Just before and after the
equivalence point, the pH
increases rapidly. At the
equivalence point, moles acid
= moles base, and the
solution contains only water
and the salt from the cation of
the base and the anion of the
acid.

68
Titration of a Strong Acid with a
Strong Base
As more base is added, the
increase in pH again levels off.

69
 Titration of a Weak Acid with a
Strong Base
Unlike in the previous case,
the conjugate base of the
acid affects the pH when it is
formed.
The pH at the equivalence
point will be >7.
Phenolphthalein is
commonly used as an
indicator in these titrations.

70
Titration of a Weak Acid with a
Strong Base

At each point below the equivalence point, the pH of the solution

during titration is determined from the amounts of the acid and its
conjugate base present at that particular time.

71
• 1. Stoichiometry problems; then
• 2. equilibrium problems to find pH
• Consider titration of 100.0 mL of 0.200 M acetic acid (Ka = 1.8 x 10 -5) by
0.100 M KOH. Calculate pH after KOH has been added:
a.0.0 mL b. 50.0 mL c. 100.0 mL
d. 150.0 mL e. 200.0 mL f. 250.0 mL
Only a weak acid is present…
HC2H3O2 ↔ H+ + C2H3O2 -

I .200M ≈0 0
C -x +x +x
E 0.200 –x x x

72
 1.8 x 10-5 = x2
0.200
x = [H+] = 1.9 x 10-3 M
pH = 2.72
b. Added OH- will react completely with the best acid present:
HC2H3O2
HC2H3O2 + OH- ↔ C2H3O2- + H2O
I .200 M x .1000L = 0.100 M x 0.050 L = 0 ----
o.0200 moles 0.00500 moles

C -0.00500 -0.00500 +0.00500

E 0.0150 mols 0 0.00500 mols

73
 • After reaction we have a buffer solution
• pH = -log (1.8 x 10-5) + log (0.00500/0.150L)
(0.0150 /0.150L)
pH = 4.74 + (-0.477) = 4.26
c. HC2H3O2 + OH- ↔ C 2H 3 O 2 - + H 2 O

I 0.200 M x 0.1000L = 0.100 M x 0.1000L = 0.0100 0

0.0200 mols moles

C -0.0100 -0.0100 +0.0100

E 0.0100 mols 0 0.0100 mols

pH = -log (1.8 x 10-5) + log (0.0100/0.200L)

(0.0100 /0.200L)
pH = 4.74

74
d. HC2H3O2 + OH- ↔ C2H3O2- + H2O
I 0.02000 0.100M x 0.150 L = 0
0.0150 mols

C -0.0150 -0.0150 +0.0150

E 0.0050 0 0.0150
pH = 4.74 + log (0.0150/0.0050)
= 5.22

75
HC2H3O2 + OH- ↔ C2H3O2 - + H2O

I 0.0200 0.100 M x 0.200 0

L = 0.0200

C -0.0200 -0.0200 +0.0200

E 0 0 0.0200 mols

**equivalence point
Moles of acid = moles of base
pH determined by conjugate base
Kb = Kw/Ka Kb = 5.6 x 10-10

76
C2H3O2- + H2O ↔ HC2H3O2 + OH-

I 0.0200/0.300 L = 0 0
0.0667 M
C -x +x +x
E 5.6
 0.0667-x
x 10-10 = x2 x x

0.0667
X= [OH-] = 6.1 x 10-6M
pOH = 5.21; pH = 8.79

77
 Since [OH-] is strong, pH is
determined by excess, conjugate
Ibase
0.0200effect is negligible
0.0250 0
CHC-0.0200 -0.0200 +0.0200
2H3O2 + OH ↔ C2H3O2 + H2O
- -

E 0 0.0050 0.0200

[OH-] = 0.0050/0.350 L
= 0.014 M
Excess pOH = 1.85
LR reactant pH = 12.15

78
Titration of a Weak Acid with a
Strong Base
With weaker acids, the initial
pH is higher and pH changes
near the equivalence point are
more subtle.

79
 Titration of a Weak Base with a
Strong Acid
• The pH at the equivalence point
in these titrations is < 7.
• Methyl red is the indicator of
choice.

80
Buffers

• Buffer exists at ½ way titration

point
• pH is stable
• Buffer @ pKa value

81
Weak vs. strong

• Buffer @ ½ way titration

• Equivalence point

82
Titrations of Polyprotic Acids

In these cases there is an

equivalence point for each
dissociation.
Also buffering at each ½
titration point.

83
• Illustrations showing the steps
used to sketch an approximate
titration curve for the titration of
50.0 mL of 0.100 M CH3COOH with
0.200 M NaOH: (a) locating the
equivalence point volume; (b)
plotting two points before the
equivalence point; (c) plotting two
points after the equivalence point;
(d) preliminary approximation of
titration curve using straight-lines;
(e) final approximation of titration
curve using a smooth curve; (f)
comparison of approximate
titration curve (solid black line) and
exact titration curve (dashed red
line).

84
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