Volumetric analysis

Volumetric(titrimetric) methods involve measuring the volume of a solution of

known concentration that is needed to react essentially completely with the analyte.

Titimetric methods are classified into four groups based on the type of reaction
involved:
 Neutralization or acid-base titrations (reaction between base and acid).
 Complex formation titrations (Ions or compounds combination to form
stable-soluble slightly dissociated ions or compounds).
 Precipitation titrations (form a simple precipitate).
 Oxidation–reduction titrations (include all reactions involving change in
oxidation number or transfer of electrons among the reaction substances).

Definition of some terms

Titration:
is a process in which a standard reagent is added to a solution of an analyte until the
reaction between them is completed.
Standard solution
is a reagent of known concentration that is used to carry out a titrimetric analysis.

 The reagent of known concentration is called the "titrant” and the substance being

titrated is termed the "titrand”.

A primary standard:
is an ultrapure compound that serves as the reference material for a titrimetric method
of analysis
Example of primary standard for titration of base is: sodium carbonate: Na2CO3
Example of primary standard for titration of acid is: potassium hydrogen iodate:
KH(IO3)2
A secondary standard: Is a standard that is prepared in the laboratory for a specific
analysis. It is usually standardized against a primary standard.

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Example of a secondary standard is the base NaOH. Commercially available NaOH
contains impurities of NaCl, Na2CO3, and Na2SO4, and readily absorbs H2O from the
atmosphere.
Equivalence point:
Is the point where the volume of added titrant at which the number of moles of titrant
is equal to the number of moles of analyte.
End point:
Is the point where the indicator changes color.
For example, suddenly change in a physical property of the solution or change the
color.
Indicator:
Is a substance that undergoes a color change when a reaction approaches completion
Titration error:
The difference between the end point and the equivalence point (it must be very
small).
 Requirements for a primary standard
1- High purity.
2- Stability toward air.
3- Absence of hydrate water.
4- Ready availability at modest cost.
5- Reasonable solubility in the titration medium.
6- Reasonable large molar mass so that the relative error associated with weighing the
standard is minimized.

 Neutralization Titrations
The standard solution employed in neutralization titrations are strong acids or strong
bases because these substances react more completely with the analyte than do their
weaker counterparts and thus yield sharper end points. Weak acids and bases never
used as standard reagents because they react incompletely with analytes.
Notes:
Acids are species that are capable of donating protons to other species.

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Bases are species that are capable of accepting protons from donor species.
Strong acids: HNO3, HCLO4, H2SO4, HCl, HI, HBr, HClO3, HBrO3.

Weak acids: H2CO3, H3BO3, H3PO4, H2S, H2SO3 and most organic acid such as
CH3COOH, CH3CH2COOH, C6H5COOH.

Strong bases: NaOH, KOH, Ba(OH)2.

Weak bases: NH4OH, Na2CO3 and most organic bases.

 Volumetric Calculations for Acid-Base Titrations
aA + bB product ; R=

titrant titrand
At equivalent point:

no. mmol of titrant (A)=no. mmol of titrand (B)

R × MA × VA = MB × VB ; = ×
. ( )

. × × ×
R × MA × VA = × =
.

no. meq of titrant (A)=no. meq of titrand (B)

NA × VA = NB × VB = ×
. ( )

. × ×
NA × VA = × =
.

% (w/w)B = ×

Note:
no. mol = M×V → V=volume (L)
= mol L-1 ×L=mol
no. mmol=M×V → V=volume (mL)
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 = × × =

Example 1:
A solution of Ba(OH)2 was standardized by titration against HCl (0.128 N).
Exactly 31.76 mL of the base were required to neutralize 46.25 mL of the acid.
What is the normality of the Ba(OH)2 solution?
Solution:
no. meq of HCl =no. meq of Ba(OH)2
NHCl × VHCl = N Ba(OH)2 × V Ba(OH)2
0.128×46.25= N Ba(OH)2 × 31.76 → N Ba(OH)2=0.1864 eq L-1
Example 2:
What volume of H2SO4(5N) is required to neutralize a solution containing 2.5g
of NaOH? M.wt NaOH=40 g mol-1
Solution:

NH2SO4 × V H2SO4 = N NaOH × V NaOH

NH2SO4 × V H2SO4 = × × V NaOH

.

. × ×
wt = ; . = = 40 g eq-1

× ×
2.5 = → V H2SO4=12.5 mL.

 Calculating the pH of strong acids and base solutions

Note:
pH=-log[H3O+] , pOH=-log[OH-] , pKw=-log[Kw]

Ion-product constant of water (Kw)=1×10-14 , pKw=14

pH + pOH= pKw , pH=14-pOH , pOH=14-pH
Example 1: Calculate the pH and pOH of 0.05M solution of HCl?

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 Solution:

[H3O+]=0.05 , pH= -log[H3O+] pH= -log[0.05]=1.3

pOH=14-1.3=12.7

Example 2: Calculate the pH and pOH of 3.2×10-4M solution of Ba(OH)2?

Solution:
Ba(OH)2 Ba2+ +2OH-
[OH-]=2×3.2×10-4 =6.4×10-4 M
pOH= -log[6.4×10-4] pOH= 3.19
pH =14 - 3.19 =10.81

 Calculating the pH of weak acids and base solutions

1-Weak acid
[H3O+]= × , Ca=concentration of acid = ( − )

2-Weak base
[OH-]= × , Cb=concentration of base = ( − )

pH=14-pOH
Example 3: Calculate the pH of 0.075 M solution of NH3, Kb=1.86×10-5 .
Solution:
[OH-]= × = √1.86 × 10 × 0.075
[OH-]=1.18×10-3 M pOH=-log1.18×10-3=2.93 pH=14-2.93=11.07
Example 4: Calculate the ionization constant of acetic acid (0.06 M) at a
specific temperature, if 1.7% of the acid solution is ionized.

Solution:

CH3COOH CH3COO- + H3O+

0.06 0 0
. . .
0.06-( × . ) ( × . ) ( × . )

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 .
[ CH3COO-]=[H3O+]= × 0.06 =0.00102 M
.
[CH3COOH]= 0.06-( × 0.06)

[CH3COOH]=0.06-0.00102=0.059M (remained)
[ ][ ] ( . )
K = = =1.76×10-5
[ ] .

 Titration of strong acid with strong base

In this titration, the titrant and analyte ionize completely since strong acid and strong
base dissociate completely. For the reaction between HCl and NaOH, the reaction is
as follows:
NaOH + HCl ↔ NaCl + H2O
Example: Let us consider the titration of 50 ml of (0.1 M) HCl with 0.1 M NaOH
solution: Calculate : pH after adding: 0,10,50,50.01ml of NaOH.
Solution:
1- To calculate pH after addition of 0 ml NaOH
pH = - log H+
pH= - log 0.1
=1
2- To calculate pH after addition of 10 ml NaOH:
. .
[H+]=

( × . ) ( × . )
[HCl] remaining =

[HCl]= =

pH= - log (4/60)

= 1.18 acidic
3- To calculate pH after addition of 50 ml of base:
Initial mmol H+ = 50 mL× 0.1 mmol/mL =5 mmol
mmol OH- added= 50 mL× 0.1 mmol/mL =5 mmol

HCl + NaOH ↔ NaCl + H2O

Initial (mmol) 5 5 0 0
Equilibrium (mmol) 0 0 5 5

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 At the equivalent point, neither HCl nor NaOH is in excess, so the
concentrations of hydronium and hydroxide ions must be equal.
[H+] = [OH-] ; Kw =[H3O+] ×[OH-] Kw =[H3O+]2
[H+] = = √1 × 10 = 1 × 10
pH= -log[H+]= -log 1 × 10 = 7
4- To calculate pH after addition of 50.01 ml of NaOH:
The addition of 50.01 ml of NaOH produces a slight excess of base in the solution,
we can obtain the pH from its concentration:
. .
[OH-]=

( × . ) ( × . )
[OH-] =
.
[OH-]= ( )
= 4.8×10-3 M

pOH = -log[OH-] = -log 0.0333 = 2.32

pH + pOH= pKw pH=14- 2.32=11.68

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