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Practical
Pharmaceutical Analytical Chemistry-1
(PC 205)
By
Staff of
Pharmaceutical Analytical Chemistry Department
Faculty of Pharmacy
Mansoura University
Contents
Subject Page
Chapter I: Introduction 4
Classification of Analytical Chemistry Branches ……………..….. 5

Standard Solutions ………………………………………………….……….…………. 7
Methods of expressing the concentration ……….…………………... 8
Chapter II: Acid-Base Titration 11
Acid-base indicators ……………………………………………………..………….. 12
Steps for the determination of a sample using titration ….….. 13
Determination of HCl sample ………………………….…………................. 14
Types of titration methods ………………………….…………………………… 15
Calculations for volumetric analysis (titration) …………..………… 16
Determination of NH4Cl sample ……..…………….…………………………. 20
Determination of NH4Cl & HCl mixture ……….……….………………… 24
Acid-base titration curve and choice of acid-base
indicators ………………..................................……………..……….……………………. 27
Determination of NaOH & Na2CO3 mixture …………………………... 30
Determination of Na2CO3 & NaHCO3 mixture ………………………. 32
Determination of Aspirin Tablets (Back titration) ….…………. 40
Determination of Boric acid (H3BO3) ………………………………......... 42
Determination of Borax (Na2B4O7) ……..………………………………..… 44
Determination of HCl & CH3COOH mixture …………………………. 45
Chapter III: Precipitation Titration 49
Introduction …………………………………………………………………………...……… 50
Mohr’s Method ………………………………………………………………………….. 51
Volhard’s Method ………………………………………………….………………….. 56
Determination of NaCl (by Volhard’s method) ……..……………… 59
Determination of KBr (by Volhard’s method) ……..…………….… 63
Determination of NaCl (by Fajan’s method) 65
2
Subject Page
Chapter IV: Complexometric Titration 67
Introduction ………………………………………………...……………..……...………….. 68
Determination of Magnesium Sulfate (MgSO4.7H2O) ……. 75
Determination of Calcium Chloride (CaCl2.6H2O) ………….… 77
Determination of Potash Alum ( KAl(SO4)2.12H2O ) ………… 78
Determination of (Ca2+/Mg2+) mixture ………………………….....……... 81
APPENDIX
Instructions for using the glassware.
3
Chapter I
Introduction
4
Analytical
Chemistry
Qualitative Analysis Analysis of Anions

(=What?)
Analysis of Cations
Quantitative Analysis
or Determination
or Estimation
or Assay
(=How much?)
Volumetric Analysis
(Titration)
Acid-base titration (Aqueous & Non-aqueous)

Precipitation titration
Complex-formation titration
Redox titration
Gravimetric Analysis
Instrumental Analysis
5
Volumetric Analysis (Titration)
Definition of Volumetric Analysis (Titration):
It is a method of quantitative analysis that depends on measuring
the volume of a solution of known concentration (standard solution)
needed to react completely with a sample of unknown concentration.
 The standard solution is placed in the burette and called "Titrant".
 The sample of unknown concentration is placed in a conical flask.
-0
Burette
(containing standard solution)
Burette
holder - 25 or 50 ml
Conical Flask
(containing sample of unknown
concentration + indicator)
6
Standard Solutions :
It is a solution of known concentration & composition.
Types of standard solutions:
1. Primary Standard Solution:
♦ It is a solution whose concentration remains constant for a long
period of time.
♦ It is prepared directly by dissolving known weight of the primary
standard substance in a certain volume of solvent.
♦ Example: Na2CO3.
2. Secondary Standard Solution:
♦ It is a solution whose concentration can be only be known
approximately.
♦ The exact concentration of it is determined by a process called
"Standardization or Standardisation".
♦ Standardization must be done after the preparation of
secondary standard solutions to determine their exact
concentration and correct any error if present. That is done by:-
Titrating the secondary standard solution against a primary
standard solution OR against a previously standardized
secondary standard.
♦ Examples: NaOH and HCl.
 Remember: Solute + Solvent = Solution
--------------------------------------------------------
7
Methods of expressing the concentration of standard solutions :
The most common methods are: Molarity (M) & Normality (N).
1. Molarity or Molar concentration (M) :
= The number of moles of the solute per 1 liter of the solution.

Example: 0.5 M NaOH means 0.5 mole of NaOH / 1 L solution.
N.B. Molar solution is a solution that contains 1 mole of the solute

per 1 liter of the solution (i.e.: Molar solution = 1 M solution).
 Remember:
Very Important
Definition of Mole (mol.):
For molecules:
The Mole means gram-molecular weight {i.e. Molecular wt. expressed in grams}.
Example: M.W. of NaOH = 40  1 mole of NaOH ≡ 40 g NaOH.
(i.e. The weight of 1 mole of NaOH is 40 g)
For atoms:
The Mole means gram-atomic weight {i.e. Atomic wt. expressed in grams}.
Example: A.W. of Na = 23  1 mole of Na ≡ 23 g Na.
(i.e. The weight of 1 mole of Na is 23 g)
2. Normality or Normal concentration (N) :
= The number of equivalent weights of the solute per 1 liter of the solution.
Example: 2 N NaOH means 2 equivalent weights of NaOH / 1 L solution.
N.B. Normal solution is a solution that contains 1 equivalent weight of
the solute per 1 liter of the solution (i.e.: Normal solution = 1 N solution).
General definition of the equivalent weight of a substance:
8
It is the weight of the substance that is equivalent in its reactive
power to 1 mole of hydrogen (i.e. the weight of the substance that will
combine with or replace 1 mole of hydrogen).
The specific definition and calculation of equivalent weight differ
according to the type of the reaction. Now, it will be studied in acid-base
reactions while other reactions will be discussed later.
Definition of Equivalent Weight in acid-base reactions:
It is the weight of the substance that will release, react with or
be chemically equivalent to 1 mole of hydrogen ions (H+) in that reaction.
How to calculate it?

M .W . of the acid
a) For acids: Equiv. wt. =
no. of replaceabl e H  in one molecule of the acid
ex: equiv. wt. of H2SO4 = M.W. of H2SO4/2 = 98/2 = 49 g H2SO4.
M .W . of the base
b) For bases: Equiv. wt. =
no. of replaceabl e OH  in one molecule of the base
ex: equiv. wt. of NaOH = M.W. of NaOH/1 = 40/1 = 40 g NaOH.
M .W . of the salt
c) For salts: Equiv. wt. =
no. of H  equivalent to one molecule of the salt
ex: equiv. wt. of CaCO3 = M.W. of CaCO3 / 2
because CaCO3 + 2 HCl CaCl2 + H2O + CO2
(i.e. 1 CaCO3 is equivalent to 2 H+).
N.B. In case of salts the number by which we divide
the M.W. of the salt is usually the sum of +ve charges on
the cation radical OR the sum of –ve charges on the anion
radical of the salt.
9
2+ 2- 3+ 3-
CaCO3 Na3PO4
Equiv. wt. = M.W. of CaCO3/2 Equiv. wt. = M.W. of Na3PO4/3
Advantage of using normal concentration: Very Important
The main advantage of using normal concentration over molar ones is
the simple 1:1 ratio involved in all reactions of the same type and that
facilitates our calculations.
ex. 1 equiv. wt. of NaOH ≡ 1 equiv. wt. of HCl i.e. In a certain type of
reactions, equivalent weights
≡ 1 equiv. wt. of H2SO4 of all substances are
equivalent in their reactive
≡ 1 equiv. wt. of H3PO4 powers because they are all
referred to a common
≡ 1 mole of H+ standard [Hydrogen].
In other words: Solutions having the same normality react in 1:1 ratio.
ex. 1 L of 1 N NaOH ≡ 1 L of 1 N HCl ≡ 1 L of 1 N H2SO4 ≡ 1 L of 1 N H3PO4 ,
10 ml of 0.2 N NaOH ≡ 10 ml of 0.2 N HCl ≡ 10 ml of 0.2 N H2SO4 ≡ 10 ml of 0.2 N H3PO4
 Remember: [=] means equal while [ ≡ ] means equivalent.
10
Chapter II
Acid-base
titration
11
Acid-Base Titrations
It's a type of titrations that involve reactions between acids and bases.
 Remember: ▪ pH = - log [H+] ……………[H+] means the molar concn. of H+.

▪ pH > 7  basic, pH =7  neutral, pH < 7  acidic.
Acid-base indicators :
♦ They are indicators used to indicate the end point of acid-base titrations
(i.e. indicate the completeness of the reaction by changing their colors).
♦ Each indicator has its specific {pH range} which is the range of pH
within which the indicator changes its color.
Examples of acid-base indicators:
1. Methyl Orange (M.O.):

 pH range ≈ (3 – 4.5) approximately.
 We use 2-3 drops of it in our experiments.

 Color:
Red Orange Yellow
pH  0 3 4.5 14
  
Acidic E.P. Basic
to M.O. by M.O. to M.O.
2. Phenolphthalein (ph.ph.):
 pH range ≈ (8.5 – 10) approximately.
 We use 10 drops of it in our experiments.

 Color:
Colorless * Pink
pH  0 8.5 10 14
  
Acidic E.P. Basic
to ph.ph.  to ph.ph.
12
*Color of ph.ph. at E.P.:
-If the solution before starting titration is Colorless (i.e. acidic to
ph.ph.)  E.P. is First Pink Color persistent for 30 seconds.
-If the solution before starting titration is Pink (i.e. basic to
ph.ph.)  E.P. is First Colorless.
 Remember:
ph.ph. (small letters) is phenolphthalein indicator
while
pH (p small, H capital) is a measure of acidity or alkalinity { = –log [H+] }
Steps for the determination of a sample

using titration
(3 steps to determine the sample concentration)
1st Preparation of the standard solution (usually HCl, H2SO4 or NaOH)
and standardization of it by titration against a primary standard
2nd Titration of the sample with the prepared standard solution and
observation of the E.P.

small f
3rd
Calculation of the sample concentration.
N.B. We say:
Titrate …………………… with or against or ≠ ……………………
in the flask in the burette

(Titrant)
13
Exp.: Determination of HCl sample
a) Preparation of 0.1 N NaOH & standardization of it.
b) Titration:
1- Transfer 10 ml of HCl sample into a clean conical flask (by bulb pipette).
2- Add 10 drops ph.ph. indicator.
3- Titrate ≠ 0.1 N NaOH (in burette).
Color change at E.P.:
from Colorless to first pink persistent for 30 sec.
c) Calculations: will be discussed later.
Repeat the experiment on another 10 ml sample
using 2 drops M.O. indicator.
from Red to Orange
14
Types of titration methods
A) Direct titration: 0
{ E.P.
It means stepwise addition of the standard solution (titrant) Standard
(titrant)
from the burette into the solution being analyzed until the end
point is reached. 10 ml sample of

unknown concn.
i.e. Sample of unknown concn. ≠ Standard (titrant)
 Vol. taken from the sample [e.g. 10 ml] ≡ (E.P.) ml of the standard
B) Residual titration OR Back titration:

In this type, a known excess of a standard (more than sufficient to
react with the sample) is added to the sample. Then after the reaction is
complete, the excess unreacted standard is back titrated against
another suitable standard.

Part reacts with the sample
i.e. Sample + known excess of standard I
Part remains unreacted
titration of the remaining unreacted part
of standard I ≠ standard II (titrant)
 E.P. ≡ remaining unreacted part
 Sample ≡ reacted part ≡ (known excess added of 1st stand. – E.P.)
The amount of the first standard that reacted with the sample can be
calculated by subtracting the volume consumed in the back titration (E.P.)
which is equivalent to the unreacted amount of the first standard from the
initially added volume (the known added excess).
15
Calculations for volumetric analysis (titration)
Volume of the standard

equivalent to the sample
(x) N or (x) M
Given:
1. Volume of the sample (= 10 ml for example).
2. Volume of the standard equivalent to the sample (End point “E.P” ).
3. Concentration of the standard (x N or x M).
Required:
Determination of the sample concentration in g/L or g%.
Solution:
The concentration of the sample can be calculated as follows:
16
Main steps of the calculations
At the beginning of calculations, you should write “balanced” chemical
equations that represent the reactions of the experiment and from
these equations find the relation between the sample and the standard.
Then the concentration of the sample can be calculated by making the
2 following steps:
1st Step: Calculation of Equivalence Factor (F)

Definition of equivalence factor:
It is the weight of the sample that is equivalent to 1 mL of the standard.
(F) is written as follows:
a x M.W. of sample x N of standard

each ml of (x) N standard ≡
b x 1000
≡ (F) g sample
≡ (F x 1000) mg sample
Where:
a = no. of moles of the sample equivalent to 1 mole of the standard.
i.e. 1 standard ≡ a sample ………… {from the reaction equations}
b = differs according to the type of the reaction:

In acid-base titration: b = no. of replaceable H+ or OH- present in
or react with ONE molecule of the
standard. (ex.: for H2SO4 → b =2).
In precipitation titration: b = no. of univalent cation atoms present in or
equivalent to ONE molecule of the standard.
(ex.: for AgNO3 → b =1, Hg(NO3)2 → b =2).
In complexometric titration: b is absent as we use molar concentrations.
In redox titration: b = electron transfer or no. of electrons lost
or gained by ONE molecule of the
standard. (ex.: for KMnO4 → b = 5).
17
Notes
1. b is absent if we use Molar concentration instead of Normal as in
the case of complexometric titrations.
2. In back (residual) titration, there are 2 standards and we can
calculate the factor (F) on any one of them but it is preferred to
calculate it on the 1st standard.
3. The concentration of standard solutions used in volumetric analysis
is usually expressed in Molarity (M) [British Pharmacopeia “BP”
and European Pharmacopeia “EP”] or Normality (N) [United
States Pharmacopeia “USP”].
2nd Step: Calculation of the Concentration

In direct titration:
E.P. x F x 1000
Concn. = = .......... g/L
Volume taken from the sample
E.P. x F x 100
= = .......... g%
In back (residual) titration:

(Known excess added from 1st standard - E.P.) x F x 1000
Concn. =
= .......... g/L
(Known excess added from 1st standard - E.P.) x F x 100

=
= .......... g%
Notes
1. Dilution factor and difference in normality or molarity should be
considered in the calculation of concentration.
2. If the original sample is Solid, {Concn. = purity}, {unit of concn.
should be g% which means g analyte/100 g of sample powder} and {we
divide by the weight taken from the sample instead of the volume}.
18
Example
Titration of 10 ml H2SO4 sample against 0.1 N NaOH, if the end point is
6 mL, calculate the concentration of H2SO4 sample (M.W. of H2SO4 = 98).
Solution:
2 NaOH + H2SO4 → Na2SO4 + 2 H2O
 1 NaOH ≡ ½ H2SO4
standard sample
Equivalence factor (F):
½ x M.W. of H2SO4 x 0.1

each ml of 0.1 N NaOH ≡ ≡ 0.0049 g H2SO4
1 x 1000
Concentration:
6 x 0.0049 x 1000
Concn. of H2SO4 = = 2.94 g/L
10
= 0.294 g%
Another example
Titration of 10 ml NaOH sample against 0.1 N H2SO4, if the end point is
4 mL, calculate the concentration of NaOH sample (M.W. of NaOH = 40).
Solution:
H2SO4 + 2 NaOH → Na2SO4 + 2 H2O
 1 H2SO4 ≡ 2 NaOH
standard sample
2 x M.W. of NaOH x 0.1

each ml of 0.1 N H2SO4 ≡ ≡ 0.004 g NaOH
2 x 1000
Concentration:
4 x 0.004 x 1000
Concn. of NaOH = = 1.6 g/L
10
= 0.16 g%
19
Exp.: Determination of NH4Cl sample
# NH4Cl is acidic because it is a salt of strong acid (HCl) & weak base (NH4OH).
# NH4Cl is determined by 2 methods:
 Back (Residual) titration method.
 Formol method [specific method for ammonium salts].
A) Determination of NH4Cl sample by back titration
Principle :
NH4Cl + NaOH  NaCl + NH3 + H20

boiling
(sample) known excess

of st. NaOH
(50 ml)
It depends upon boiling the ammonium salt with a known excess of
standard alkali (NaOH) producing ammonia which is removed by boiling.
Then the remaining unreacted part of NaOH is back titrated against
standard HCl using M.O. or ph.ph. indicator.
NaOH + HCl 
 NaCl + H20
remaining standard
unreacted titrant
part
Notes:
1) Boiling is necessary for the reaction between NH4Cl and NaOH to
remove the produced ammonia.
2) This method requires Blank Determination which is a separate
determination in which we repeat the same steps of the experiment
but without the sample and the E.P. in this case is called
Blank Reading.
20
 Blank determination is required in this experiment because
when NaOH is heated and then cooled, its strength is decreased due to:
1- Interaction of NaOH with the glass of the flask.
2- Absorption of atm. CO2.
More explanation about blank determination:
Sample + 50 ml 1 N NaOH 
 50 ml of 1 N NaOH 


x ml
Boil
Main experiment
   
part remaining
Cool
loss due to reactn. with glass & CO2

reacted unreacted part

with the (x ml)
titrate the remaining sample 
unreacted part of 1 N NaOH Titr. ≠ 1 N HCl
≠ 1 N HCl 
 [E.P. = x ml]
E.P.
50 ml 1 N NaOH 
 50 ml of 1 N NaOH 


Blank determination
Boil
  
remaining unreacted part
Cool loss due to reactn. with glass & CO2

 Titr. ≠ 1 N HCl
titrate the remaining 
unreacted part of 1 N NaOH the volume consumed from
≠ 1 N HCl titrant (1 N HCl) is called
 [Blank reading]
ex: 49.8, 49.9...etc
Blank reading
 The part reacted with the sample = (Blank reading – E.P.)
21
Procedure :
1) Transfer 10 ml of NH4Cl sample into a clean conical flask. (by bulb pipette 10 ml)
2) Add 50 ml of 1 N NaOH. (by bulb pipette 25 ml "2 times")
3) Boil for 10 min. inserting a funnel in the neck of the flask to avoid
evaporation of the solution.
After boiling, ensure that no more NH3 is produced indicated by
the disappearance of ammonia odor.
4) Cool.
5) Add 2 drops M.O. indicator.
6) Titrate ≠ 1 N HCl.
{ Color change at E.P.: from Yellow to Orange }
Calculations :
NH4Cl + NaOH  NaCl + NH3 + H20
boiling
1st standard
NaOH + HCl 
 NaCl + H20
2 nd standard
The equivalence factor (F) can be calculated on NaOH (1st standard) or on
HCl (2nd standard) but it is preferred to be calculated on the 1st standard.
Calculation of equivalence factor (F):
1 NaOH ≡ 1 NH4Cl
standard sample
1 x M.W. of NH4Cl x 1
each ml of 1 N NaOH ≡ ≡ ..................... g NH4Cl
1 x 1000
Calculation of concentration:
(Blank reading – E.P.) x F x 1000

Concn. of NH4Cl = = ................... g/L
10
Results:
E.P. =
Concn. =
22
B) Determination of NH4Cl sample by formol method
Principle :
4 NH4Cl + 6 HCHO 
 (CH2)6N4 + 4 HCl + 6 H20
(sample) neutral Hexamine
formalin or Equivalent
Hexamethylene to NH4Cl
tetramine sample
It depends upon the addition of HCHO to the ammonium salt
resulting in the formation of Hexamine (Hexamethylene tetramine)
in addition to an amount of HCl equivalent to the sample analysed.
Then the produced HCl is titrated ≠ standard NaOH using ph.ph.
indicator.
4 HCl + 4 NaOH 
 4 NaCl + 4 H2O
 4 NH4Cl ≡ 4 HCl ≡ 4 NaOH
23
Exp.: Determination of NH4Cl & HCl mixture
Our target is to determine the concentration of each component of the mixture
Principle :
a) For HCl only: (E.PHCl)
HCl only is determined by direct titration of the mixture against
standard NaOH using M.O. indicator.
(NH4Cl does not interfere because it needs boiling to react with NaOH).
b) For the total mixture [NH4Cl & HCl]: (E.Ptotal)
The determination of the total depends on the addition of neutral
formalin (HCHO) to the mixture where it reacts with NH4Cl leading
to the production of an equivalent amount of HCl {Formol method}.
 (CH2)6N4 + 4 HCl + 6 H20
(sample) neutral Hexamine
formalin or Equivalent
Hexamethylene to NH4Cl
tetramine sample
Then both (HCl) produced from NH4Cl and (HCl) originally present in the
mixture are directly titrated ≠ standard NaOH using ph.ph. indicator.

NH4Cl & HCl

HCl both are titrated ≠ standard NaOH
 NH4Cl only ≡ (E.Ptotal - E.PHCl)
Procedure :
a) For HCl only: (E.PHCl)
1) Transfer 10 ml of the mixture into a clean conical flask.
3) Titrate ≠ 0.1 N NaOH.
24
{ Color change at E.P.: from Red to Orange }
b) For the total mixture [NH4Cl & HCl]: (E.Ptotal)
1) Transfer another 10 ml of the mixture into a clean conical flask.
2) Add 5 ml neutral formalin. (by measuring cylinder )
!!!!!! Caution: Formalin is very toxic !!!!!!

3) Leave for 5 minutes. (to make the reaction completed)
4) Add 10 drops ph.ph. indicator.
from Colorless to first pink persistent for 30 sec.
Calculations :
E.PHCl ≡ HCl only
E.Ptotal ≡ HCl + NH4Cl
 (E.Ptotal - E.PHCl) ≡ NH4Cl only
For HCl :
HCl + NaOH 
 NaCl + H20
 1 NaOH ≡ 1 HCl
standard sample
1 x M.W. of HCl x 0.1

each ml of 0.1 N NaOH ≡ ≡ .......... g HCl
1 x 1000
Concentration:
E.PHCl x F x 1000
Concn. of HCl = = .......... g/L
10
For NH4Cl :
 (CH2)6N4 + 4 HCl + 6 H20
25
4 HCl + 4 NaOH 
 4 NaCl + 4 H2O
 4 NH4Cl ≡ 4 HCl ≡ 4 NaOH
 1 NaOH ≡ 1 NH4Cl
standard sample
# Note that formalin (HCHO) is not standard
1 x M.W. of NH4Cl x 0.1

each ml of 0.1 N NaOH ≡ ≡ .......... g NH4Cl
1 x 1000
Concentration:
(E.Ptotal - E.PHCl) x F x 1000

Concn. of NH4Cl = = .......... g/L
10
Results:
E.PHCl =
E.Ptotal =
Concn. of HCl =
Concn. of NH4Cl =
26
Acid-Base Titration Curve
and Choice of Acid-Base Indicators
♦ Introduction :(Definitions of some terms)
The Equivalence Point The End Point
[Theoretical] [Experimental]
- It is the point at which the added - It is the point at which the visual
amount of the standard solution is change of the indicator takes
chemically equivalent to the amount place in the titration.
of the substance being determined.
- Its real position can only be - Its position can be determined
theoretically calculated. experimentally.
- It is expressed by the volume of - It is expressed by the volume of
the titrant added. the titrant added.
The Titration Error
It is the difference between the equivalence point and the end point.
The more accurate the titrimetric method, the smaller the titration error.
 The Titration Curve of Acid-Base titrations:

It is the curve obtained by plotting the pH of
pH
the titrated solution (y-axis) against the volume
of the titrant added (x-axis).
The titration curve is characterized by a Sigmoid Equivalence mls added

point of the titrant
shape and the midpoint of the vertical part of the
curve corresponds to the equivalence point.
27
How to predict the shape of the titration curve?
End of the curve

pH of If higher predicted from
the titrated concn. pH of the titrant
solution
If lower
concn.
Middle of the curve

predicted from
pH of the products
(= pH at equivalence point)
Start of the curve

predicted from mls added
pH of the sample of the titrant
 The pH-range of the indicator:
It is the pH-range ( pH-interval ) within which the indicator changes
its color.
Ex.: - The pH-range of M.O. ≈ (3 – 4.5) approximately.
- The pH-range of ph.ph. ≈ (8.5 – 10) approximately.
♦ Choice of acid-base indicators :
For accurate titrimetric method, the indicator should be selected so as
to make the titration error small as possible. To achieve that the pH-range
of the indicator should fall in the vertical part of the titration curve (i.e.
the part marked by sharp change of pH) because the equivalence point is
28
located in this part so the difference between (the equivalence point) and
(the end point indicated by the selected indicator) will be small as possible.
Example:
Titration of NaOH with standard HCl using M.O. or ph.ph. indicator:
NaOH + HCl  NaCl + H2O pH
(pH = 7)
The calculated equivalence point pH range of ph.ph.
corresponds to pH=7.
7
But since the vertical part of this
titration curve ranges from about pH range of M.O.
3.5 to 10.5 so either M.O. (3 – 4.5)
or ph.ph. (8.5 – 10) can be used as Equivalence

Point
M.O. End
Point
mls added of
(Theoretical) (Experimental) standard HCl
indicator for this titration. Titration Error
(very small)
29
Exp.: Determination of NaOH & Na2CO3 mixture
Principle :
 According to the two-indicators method:
a) First step: (E.Pph.ph.)
Titration of 10 ml of the mixture ≠ standard HCl using ph.ph. indicator.

1
E.Pph.ph. ≡ OH- + CO3--
2
b) Second step: (E.PM.O.)
Titration of another 10 ml of the mixture ≠ standard HCl using M.O. ind.
E.PM.O. ≡ OH- + CO3--
 Reaction equations:
For NaOH:
NaOH + HCl → NaCl + H2O
For Na2CO3:
Na2CO3 + HCl → NaCl + NaHCO3 ...................Half neutralization

(pH>10) (pH ≈ 8.3)
NaHCO3 + HCl → NaCl + CO2 + H2O ...............Complete neutralization

(pH ≈ 3.8) .
Na2CO3 + 2HCl → 2NaCl + CO2 + H2O
Procedure :
1 E.Pph.ph. :
3) Titrate ≠ 0.2 N HCl.
{ Color change at E.P.: from Pink to Colorless }

30
2 E.PM.O. :
Calculations :
1
E.P1 (ph.ph.) ≡ OH- + CO3--
2
E.P2 (M.O.) ≡ OH- + CO3--
1
 (E.P2 - E.P1) ≡ CO3--
2
 2(E.P2 - E.P1) ≡ CO3--
 [E.P2 - 2(E.P2 - E.P1)] ≡ OH-

For NaOH :
NaOH + HCl 
 NaCl + H20
 1 HCl ≡ 1 NaOH
standard sample
1 x M.W. of NaOH x 0.2

each ml of 0.2 N HCl ≡ ≡ .......... g NaOH
1 x 1000
Concentration:
[E.P2 - 2(E.P2 - E.P1)] x F x 1000

Concn. of NaOH = = .......... g/L
10
For Na2CO3 :
 2 HCl ≡ 1 Na2CO3
standard sample
1
 1 HCl ≡ Na2CO3
standard
2 sample

31
1
x M.W. of Na2CO3 x 0.2
2
each ml of 0.2 N HCl ≡ ≡ .......... g Na2CO3
1 x 1000
Concentration:
2(E.P2 - E.P1) x F x 1000

Concn. of Na2CO3 = = .......... g/L
10
Results:
E.P1 =
E.P2 =
Concn. of NaOH =
Concn. of Na2CO3 =
32
Exp.: Determination of Na2CO3 & NaHCO3 mixture
Principle :
1) First step: (E.Pph.ph.)
Titration of 10 ml of the mixture ≠ standard HCl using ph.ph. indicator.

1
E.Pph.ph. ≡ CO3--
2
2) Second step: (E.PM.O.)
Titration of another 10 ml of the mixture ≠ standard HCl using M.O. ind.
E.PM.O. ≡ CO3-- + HCO3-
For Na2CO3:
Na2CO3 + HCl → NaCl + NaHCO3 ...................Half neutralization

(pH>10) (pH ≈ 8.3)
NaHCO3 + HCl → NaCl + CO2 + H2O ...............Complete neutralization

(pH ≈ 3.8) .
For NaHCO3:
NaHCO3 + HCl → NaCl + CO2 + H2O
N.B.:
The reaction between HCl & Na2CO3 or between HCl & NaHCO3 is
an example of displacement titration where HCl (strong acid) displaces
carbonic acid (very weak acid) in its salts.
33
Procedure :
1 E.Pph.ph. :
2 E.PM.O. :
Calculations :
1
E.P1 (ph.ph.) ≡ CO3--
2
E.P2 (M.O.) ≡ CO3-- + HCO3-
 2E.P1 ≡ CO3--
 (E.P2 - 2E.P1) ≡ HCO3-

For Na2CO3 :
 2 HCl ≡ 1 Na2CO3
standard sample
1
 1 HCl ≡ Na2CO3
2
standard sample
1
x M.W. of Na2CO3 x 0.2
2
each ml of 0.2 N HCl ≡ ≡ .......... g Na2CO3
1 x 1000
34
Concentration:
2E.P1 x F x 1000
Concn. of Na2CO3 = = .......... g/L
10
For NaHCO3 :
NaHCO3 + HCl → NaCl + CO2 + H2O
 1 HCl ≡ 1 NaHCO3
standard sample
1 x M.W. of NaHCO3 x 0.2

each ml of 0.2 N HCl ≡ ≡ .......... g NaHCO3
1 x 1000
Concentration:
(E.P2 - 2E.P1) x F x 1000

Concn. of NaHCO3 = = .......... g/L
10
Results:
E.P1 =
E.P2 =
Concn. of Na2CO3 =
Concn. of NaHCO3 =
35
Illustrative diagrams for the titration of
NaOH ≠ standard HCl
Na2CO3 ≠ standard HCl
NaHCO3 ≠ standard HCl
36
8.3 - 8.3 -
3.8 - 3.8 -
37
8.3 - 8.3 -
3.8 - 3.8 -
38
Summary
OH- CO3-- HCO3-
E.Pph.ph. 1
all OH- CO3-- No E.P.
(1st flask): 2
E.PM.O.
all OH- all CO3-- all HCO3-
(2nd flask):
39
Exp.: Determination of Aspirin tablets (Back titration)
Principle : (Back or Residual Titration)
known excess
Aspirin (sample) of st. NaOH Sod. acetate Sod. salicylate
(50 ml)
The method depends on boiling aspirin (acetylsalicylic acid) with
a known excess of standard alkali (NaOH) where aspirin is hydrolysed into
acetic and salicylic acids which react with sodium hydroxide giving sodium
acetate and sodium salicylate. Then the remaining unreacted part of
NaOH is back titrated against standard HCl using ph.ph. indicator.
NaOH + HCl 
 NaCl + H20
remaining standard
unreacted titrant
part
Notes:
This method requires Blank Determination which is a separate
determination in which we repeat the same steps of the experiment but
without the sample and the E.P. in this case is called Blank Reading.
Procedure :
1) Transfer 1 Rivo tablet (equivalent to 320 mg acetylsalicylic acid) into
a clean flask.
2) Add 50 ml of 0.1 N NaOH.
3) Boil for 10 minutes inserting a funnel in the neck of the flask
to avoid evaporation of the solution.
4) Cool and add 10 drops ph.ph. indicator.

40
Calculations :
1st standard
Aspirin (sample)
NaOH + HCl 
 NaCl + H20
2 nd standard
The equivalence factor (F) can be calculated on NaOH (1st stand.) or
on HCl (2nd stand.) but it is preferred to be calculated on the 1st standard.
Calculation of equivalence factor (F):
2 NaOH ≡ 1 Aspirin
standard sample
1
 1 NaOH ≡ Aspirin
standard
2 sample
1
x M.W. of Aspirin x 0.1
2
each ml of 0.1 N NaOH ≡ ≡ .......... g Aspirin
1 x 1000
(Blank reading – E.P.) x F x 100

Concn. (Purity) of Aspirin = = ........ g%
0.320
Results:
E.P. =
Concn. (Purity) of Aspirin =
The Pharmacopoeial limits for the purity of aspirin:
 According to BP 2007: from 95.0% to 105.0%.
 According to USP 2007: from 90.0% to 110.0%.
41
Exp.: Determination of Boric acid (H3BO3)
Principle :
Boric acid (H3BO3) is a very weak monoprotic acid (pKa = 9.2) so it
can not be titrated against a standard alkali.
H3BO3 BO2- + H+ + H2O

metaborate ion
But if a sufficient amount of Glycerol, Mannitol or similar organic
polyhydroxy compound is added to boric acid, it will be converted into
a relatively stronger monoprotic acid that can be directly titrated
against standard NaOH using ph.ph. indicator.
(very weak acid) (relatively stronger acid)

{ pH near 7 } { pH ≈ 4.2 }
[Glyceroboric complex] H + NaOH  [Glyceroboric complex] Na + H2O
Notes:
1) The reaction between glycerol and boric acid may be 2:1 (as shown in
the above equation) or 1:1 (as shown in the following equation):
2) M.O. indicator is unsuitable for the titration of glyceroboric acid
against NaOH because the pH of glyceroboric acid is about 4.2

42
(i.e. the titration curve will start at pH 4.2 and go upward) so the
vertical part of the titration curve will be above the pH-range of M.O.
3) If the titration is done directly on boric acid without adding glycerol,
the end point will appear very rapidly due to the hydrolysis of the
produced sodium metaborate leading to the formation of NaOH again
giving pink color with ph.ph.
H3BO3 + NaOH NaBO2 + 2H2O

Sod. metaborate
Procedure :
1) Transfer 10 ml of the sample into a clean conical flask.
2) Add 5 ml neutral glycerol
4) Titrate ≠ 0.1 N NaOH. {Color change at E.P. from colorless to pink }
Calculations :
Boric acid + 2 glycerol  [Glyceroboric complex] H + 3H2O
[Glyceroboric complex] H + NaOH  [Glyceroboric complex] Na + H2O

titrant
 1 Boric acid ≡ 1 glyceroboric acid ≡ 1 NaOH
 1 NaOH ≡ 1 Boric acid

standard sample
1 x M.W. of boric acid x 0.1

each ml of 0.1 N NaOH ≡ ≡ ........ g boric à
1 x 1000
Concentration:
E.P x F x 1000
Concn. of boric acid = = .......... g/L
10
43
Exp.: Determination of Borax (Na2B4O7)
(Borax = Sodium Borate = Sodium Tetraborate)
Principle :
# Borax is hydrolyzed in water as follows:
Na2B4O7 + 7 H2O  2 NaOH + 4 H3BO3
Tit. ≠ add
glycerol
0.1 N HCl
Tit. ≠
0.1 N NaOH
The liberated NaOH can be titrated against 0.1 N HCl using M.O. indicator
without interference of boric acid as it is a very weak acid.
Procedure :
3) Titrate ≠ 0.1 N HCl. {Color change at E.P: from Yellow to Orange }
Calculations :
Na2B4O7 + 7 H2O  2 NaOH + 4 H3BO3
2 NaOH + 2 HCl  2 NaCl + 2 H2O
titrant
 1 Borax ≡ 2 NaOH ≡ 2 HCl

1
 1 HCl ≡ Borax
standard 2 sample
1
x M.W. of borax x 0.1
each ml of 0.1 N HCl ≡ 2 ≡ .......... g borax
1 x 1000
Concentration:
E.P x F x 1000
Concn. of borax = = .......... g/L
10
44
Exp.: Determination of HCl & CH3COOH mixture
Principle :
a) First step: (E.PM.O.)  for HCl only
Titration of 10 ml of the mixture ≠ standard NaOH using M.O. indicator.
E.PM.O. ≡ HCl only
b) Second step: (E.Pph.ph.)  for Total (HCl & CH3COOH)
Titration of another 10 ml of the mixture ≠ standard NaOH using ph.ph. ind.
E.Pph.ph. ≡ HCl + CH3COOH
HCl + NaOH → NaCl + H2O
CH3COOH + NaOH → CH3COONa + H2O
Notes:
1) During the determination of HCl only (1st E.P. using M.O.): NaOH neutralizes
HCl only without interference of acetic acid because the hydrogen
ion (H+) of HCl suppresses the ionization of acetic acid by common-ion
effect as shown in the following equations:
HCl 
 H+ + Cl-
CH3COOH 
 H+ + CH3COO-
and when the neutralization of HCl is completed, the pH of the solution
reaches the pH-range of M.O. and so M.O. changes its color.
While during the detn. of total HCl & acetic acid (2nd E.P. using ph.ph.):
NaOH neutralizes HCl first without any change in the color of ph.ph.
and then the titration is completed to make neutralization of acetic

45
acid also. At this point, the pH reaches the pH-range of ph.ph. and so
ph.ph. changes its color.
Question: (Complete the following)
In the detn. of (HCl/CH3COOH) mix. ≠ NaOH, E.PM.O. is lower than E.Pph.ph.
while in the detn. of Na2CO3 ≠ HCl, E.PM.O. is higher than E.Pph.ph. provided
that the 2 end points are done on 2 separate flasks.
2) The principle of this determination can be applied for the
determination of many (Strong acid/Weak acid) mixtures where:
E.PM.O. ≡ Strong acid
E.Pph.ph. ≡ Total (Strong acid + Weak acid)
Examples of strong acids: HCl, H2SO4
Examples of weak acids: Acetic acid (CH3COOH), Butyric acid (C3H7 COOH),
Phthalic acid ( ).
1
Note: In case of H2SO4 or Phthalic acid  a = (when calculating F).
2
46
Procedure :
A M.O. reading (E.P1) :
{ Color change at E.P.: from Red to Orange }
B ph.ph. reading (E.P2) :
{ Color change at E.P.: from Colorless to first Pink persistent for 30 sec.}
Calculations :
E.P1 (M.O. reading) ≡ HCl only
E.P2 (ph.ph. reading) ≡ HCl + CH3COOH
 (E.P2 - E.P1) ≡ CH3COOH only
For HCl :
HCl + NaOH   NaCl + H20
 1 NaOH ≡ 1 HCl
standard sample
1 x M.W. of HCl x 0.1

each ml of 0.1 N NaOH ≡ ≡ .......... g HCl
1 x 1000
Concentration:
E.P1 x F x 1000
Concn. of HCl = = .......... g/L
10
For CH3COOH :
47
CH3COOH + NaOH 
 CH3COONa + H20
 1 NaOH ≡ 1 CH3COOH
standard sample
1 x M.W. of CH3COOH x 0.1
each ml of 0.1 N NaOH ≡ ≡ ..... g CH3COOH
1 x 1000
Concentration:
(E.P2 - E.P1) x F x 1000

Concn. of CH3COOH = = .......... g/L
10
Results:
E.P1 =
E.P2 =
Concn. of HCl =
Concn. of CH3COOH =
48
Chapter III
Precipitation titration
49
Precipitation Titration
Introduction :
 Definition of Precipitation Titration:

It is a type of volumetric analysis that depends on the formation of
a precipitate.
 Precipitation Titration
= Precipitimetric Titration
= Precipitate-formation Titration.
 The most important precipitating agent used in precipitation titration
is Silver Nitrate (AgNO3).
 Titrimetric methods based upon using silver nitrate (AgNO3) are
called Argentometric titration.
 Argentometric titrations are mainly used for determination of halides

(Cl-, Br- & I-). It is also used for the determination of SCN-, CN- and
some compounds that form insoluble products (ppt) with AgNO3.
Types of Precipitation Titration :
Precipitation titrations are classified into 3 main types according to
the method of detection of end point:
1. Volhard's method  depends on the formation of
Colored complex ions (Colored solution).
2. Fajan's method  depends on the formation of
Colored adsorption compound.
3. Mohr's method  depends on the formation of
Colored secondary precipitate.
50
Mohr's Method .
It is a type of precipitation titration that depends on the formation of
a colored secondary ppt at the end point.
Main features of Mohr's method:
 Sample: Cl- , Br- (Not for I- or SCN-).
 Type of titration: Direct titration.
 Standard Solution: Standard AgNO3.
 pH: Neutral or slightly alkaline. (pH ≈ 6.5 -9).
 Indicator: 1 ml of 5% Pot. Chromate (K2CrO4)

solution.
 Color at E.P.: First permanent darkening of the yellow

chromate color [due to the formation of
Ag2CrO4 (brick red ppt) at the end point
leading to darkening of the solution].
51
Exp.: Determination of NaCl by Mohr's method
Principle :
It depends on the titration of NaCl sample with standard AgNO3 using
potassium chromate (K2CrO4) as indicator.
Titration reaction:
Cl- + Ag+  AgCl 

sample titrant white ppt
End point reaction:
2 Ag+ + CrO4--  Ag2CrO4 

titrant indicator brick red ppt
In this experiment, Cl- sample is titrated with Ag+ in presence of CrO4--
indicator where AgCl is precipitated as a white ppt before Ag2CrO4 THEN
at the end point (i.e. when Cl- is completely reacted with Ag+), the first
slight excess of Ag+ will react with CrO4-- indicator giving Ag2CrO4 (brick
red ppt) leading to darkening of the yellow color of the solution.
Notes:
3) Effect of pH: Mohr's method should be done in neutral or slightly
alkaline medium (pH ≈ 6.5 -9) because:
At pH  9: Ag+ will be precipitated as AgOH (brown to black ppt)

leading to Consumption of the titrant & Masking of the E.P. color.
Ag+ + OH-  AgOH  (brown to black ppt)
While at pH  6.5: The chromate ion (CrO4--) changes into acid chromate
(HCrO4-) then to dichromate (Cr2O7--). Both HCrO4- & Cr2O7-- form soluble
salts with Ag+ & so no colored ppt will be formed at the E.P.
2 CrO4-- + 2 H+  2 HCrO4-  Cr2O7-- + H2O
chromate acid chromate dichromate
52
4) Ag2CrO4 is more soluble than AgCl so that No Ag2CrO4 will be
precipitated until all Cl- ions have been precipitated as AgCl provided
that the CrO4-- concentration should be adjusted to make Ag2CrO4
formed only at the end point and so prevent error in the end point.
1 ml of 5% K2CrO4 solution is suitable.
High concentration of K2CrO4  gives too soon (early) E.P.
because Ag2CrO4 will be rapidly precipitated before E.P.
Low concentration of K2CrO4  gives too late E.P.
because CrO4-- will be insufficient and so a large amount of
Ag+ (titrant) will be needed to precipitate Ag2CrO4 and so the E.P.
comes too late.
5) I- & SCN- can not be determined by Mohr's method because the
formed AgI & AgSCN strongly adsorb CrO4-- on their surfaces and so
the ppt formed at the end point will be an adsorption compound which
is less colored and so less sharp E.P. will be obtained.
6) BLANK EXPERIMENT should be done because: An additional excess
of AgNO3 (titrant) will be added after the correct E.P. to form
enough Ag2CrO4 to be seen over the heavy white ppt of AgCl & the
yellow color of K2CrO4 indicator leading to error (increase) in the end
point. This error can be corrected by performing blank determination
to know the volume of the additional excess of AgNO3 (titrant) that
causes error.
In blank determination, all steps of the experiment are performed in
absence of sample but using 10 ml dist. water instead of it and also
using talc or CaCO3 powder to imitate (‫ )تحاكي‬the white AgCl ppt.
i.e. 10 ml dist. water + 1 ml 5% K2CrO4 + talc or CaCO3 powder 
titate  st. AgNO3 till the 1st darkening of the yellow chromate color.
53
The volume consumed of AgNO3 (titrant) is called Indicator Blank
and it should be subtracted from the observed E.P. in the original
experiment.
{ i.e. the calculation of concentration involves (E.P. - Ind. Blank)}.
Procedure :
5) Add 1 ml of 5% K2CrO4 indicator (by graduated pipette).
6) Titrate ≠ 0.01 N AgNO3
{ Color at E.P.: 1st permanent darkening of the yellow chromate color }
Before starting tit.: Cl- sample + CrO4-- ind.  Clear bright

(colorless) (yellow color) yellow solution
During tit. ≠ AgNO3: AgCl + Cl- sample + CrO4-- ind.  Turbid bright
(white ppt) (colorless) (yellow color) yellow solution
At the end point: AgCl + CrO4-- ind. + Ag2CrO4  Turbid dark

(white ppt) (yellow color) (brick red ppt)
few
yellow solution
Calculations :
Calculations in precipitation titration differ from that in acid-base titration in
the calculation of equivalence factor where (b) in precipitation titration equals
the number of univalent cation atoms present in or equivalent to ONE molecule
of the standard. In other words, (b) equals the total positive charge on the
cation radical of ONE molecule of the standard.

+1 +1 +2
ex.: For AgNO3  b = 1, For NH4SCN  b = 1, For Hg(NO3)2  b = 2
For this experiment:
Cl- + Ag+  AgCl 
54
 1 AgNO3 ≡ 1 NaCl
standard sample
1 x M.W. of NaCl x 0.01
each ml of 0.01 N AgNO3 ≡ ≡ .......... g NaCl
1 x 1000
Concentration:
(E.P.- Ind. blank) x F x 1000
Concn. of NaCl = = .......... g/L
10
Results:
E.P. =
Concn. =
55
Volhard's Method .
It is a type of precipitation titration that depends on the formation of
colored complex ions (colored solution) at the end point.
Main features of Volhard's method:
 Sample: Cl- , Br-, I- & SCN-.
 Type of titration: Back (Residual) titration.
 1st standard (25 ml): AgNO3.

 Standard Solutions:
 2nd standard (titrant): NH4SCN or KSCN.
 pH: Acidic medium (HNO3).
 Indicator: Ferric salts such as:
1) Ferric alum = Ferric ammonium Sulfate

{ FeNH4(SO4)2.12H2O }.
OR 2) Ferric nitrate { Fe(NO3)3 }.
 Color at E.P.: Faint orange or faint red color.
56
Introduction on Solubility Product (Ksp) :
♦ Ksp is calculated only for sparingly soluble salts (ex.: AgCl) and it is
constant for a certain salt at a specified temperature.
(ex.: Ksp of AgCl = 1.8x10-10, AgBr
♦ Meaning of Ksp:
For AgCl (for example): Ksp = [Ag+][Cl-]……at saturated solution (or at equilibrium).
♦ Ksp values for a certain salt can be known from reference tables.
♦ Significance of Ksp:
 For the ppt of AgCl (for example) to be formed in a solution:
[Ag+][Cl-] must be  Ksp of AgCl.
 For different sparingly soluble salts:
 Solubility product (Ksp) ≡  Solubility ………. & vice versa.
 If different precipitates can be formed:
 Ksp ≡ the salt is precipitated first (i.e: the salt is more insoluble or less soluble).
≡ more stable ppt.
N.B.: This rule is not always obeyed in case of non-symmetrical
salts (i.e. salts in which the valence of the cation radicle  the valence
of the anion radicle) such as Ag2CrO4 , PbI2 ......etc.
{although Ksp of Ag2CrO4 is less than Ksp of AgCl but Ag2CrO4 is more
soluble than AgCl…………refer to Mohr's method}.
57
Important example:
Ksp of AgI  AgBr  AgSCN  AgCl
So:
 If a mix. of I-, Br-, SCN-, Cl- (of near concentrations) is treated with Ag+:
+ Ag+
The order of precipitation will be:

1- AgI
2- AgBr
3- AgSCN
4- AgCl
 If we have:
AgCl ppt AgBr ppt AgI ppt
+ SCN- + SCN- + SCN-
AgSCN ppt No reaction No reaction

+ Cl-
58
Exp.: Determination of NaCl by Volhard's method
Principle : {Back (Residual) titration}
It depends upon the precipitation of Cl- as AgCl by the addition of
a known excess of standard AgNO3 THEN the remaining unreacted AgNO3 is
back titrated against standard NH4SCN using ferric alum indicator.
1 Cl- + Ag+ 
 AgCl 
(sample) (25 ml st. AgNO3) white ppt
2 Titration reaction: NH4SCN titrant
Ag+ + SCN- 
 AgSCN 
(remaining unused excess) (NH4SCN titrant) white ppt
3 End point reaction: remaining unused AgNO3

+ Fe3+ indicator
SCN- + Fe3+ 
 [Fe(SCN)]2+
(1st dr. excess after complete (indicator) faint orange
reactn with the unused Ag+) or faint red color
Notes:
1) Since Ksp of AgSCN  AgCl so AgSCN is more stable (more insoluble)
than AgCl so after complete reaction between NH4SCN titrant & the
excess unused AgNO3, the SCN- ions will attack AgCl ppt and replace Cl-:
AgCl (solid) + SCN- 
 AgSCN (solid) + Cl-
To overcome this problem: The ppted AgCl must be removed or coated before
titrating the excess unused Ag+ with NH4SCN & that can be achieved by:
1- Filtration of AgCl ppt before titration.
OR 2- Coating AgCl ppt by the addition of an organic solvent as
nitrobenzene or amyl alcohol which forms a water-proof layer
around AgCl ppt protecting it from reaction with NH4SCN.
In the detn. of NaCl by Volhard's method, if AgCl is not removed,
the observed E.P. will be higher than the true and the calculated Cl - content
(concn.) will be lower than the true... because it's a back titration.
59
2) Strong shaking near the E.P. is required to prevent adsorption of Ag+ ions
on the freshly ppted AgSCN which leads to occurrence of early E.P.
In the detn. of NaCl by Volhard's method, if the titration is done without
vigorous shaking at the E.P., the observed E.P. will be lower than the true and
the calculated concn. will be higher than the true.
3) The titration is performed only in acidic medium (HNO3) because:

a. In alkaline medium, Ag+ & Fe3+ ions will be ppted as AgOH &
Fe(OH)3.
b. HNO3 prevent precipitation of other Ag+ salts like carbonate
and sulfide because these salts are soluble in HNO3.
c. HNO3 helps the coagulation of AgCl ppt & that facilitates its
filtration or coating.
BUT too high concentration of HNO3 should be avoided because that
destroys the colored ferric thiocyanate complex formed at the E.P.
Required Glassware:
 100-ml measuring (volumetric) flask . well-closed
 Stoppered flask.  well-closed
 Conical flask.
 Burette & burette holder.
 10-ml bulb pipette.
 25-ml bulb pipette.
 10-ml graduated pipette.
 10-ml measuring cylinder.
 Filter papers (Whatmann no.1).
 Funnel.
 Beaker.
 Dropper.
 Calculator.
60
Procedure :
!!! BEFORE STARTING THE DETERMINATION,
WASH ALL THE GLASSWARE WITH DISTILLED WATER.
(because tap water contains Cl -).
1 Transfer accurately 10 ml of the sample into a 100-ml measuring flask.
2 Add 2 ml conc. HNO3.
3 Add 25 ml of 0.05 N AgNO3.
4 Shake well for few minutes to coagulate the precipitated AgCl.
5 Complete to the mark with distilled water.
6 Mix well.
7 Filter through a dry filter paper, rejecting the first few milliliters of
the filtrate.
8 Transfer 25 ml of the filtrate into a clean glass stoppered flask.
9 Add 1 ml ferric alum indicator.
10 Titrate with 0.01 N NH4SCN with strong shaking.
Color at E.P.: Faint Orange Color not disappear on strong shaking.
61
Calculations :
In this exp., the equivalence factor (F) can be calculated on 0.05 N AgNO3
(1st standard "25 ml") OR on 0.01 N NH4SCN (2nd standard "titrant") but it is
preferred to be calculated on the 1st standard.
If (F) is calculated on the 1st standard (0.05 N AgNO3):
1 AgNO3 ≡ 1 NaCl
standard sample

each ml of 0.05 N AgNO3 ≡ ≡ .......... g NaCl
1 x 1000
0.05 N 0.01 N 0.05 N
[25 – 4 E.P. ( 0.01 )] x F x 1000

Concn. = 0.05 = .......... g/L
10
Dilution
factor
If (F) is calculated on the 2nd standard (0.01 N NH4SCN):

1 NH4SCN ≡ 1 NaCl
standard sample

each ml of 0.01 N NH4SCN ≡ ≡ .......... g NaCl
1 x 1000
0.05 N 0.01 N 0.01 N
[25 ( 0.05 ) – 4 E.P.] x F x 1000

Concn. = 0.01 = .......... g/L
10
Dilution
factor
Results:
E.P. =
Concn. =
62
Exp.: Determination of KBr by Volhard's method
Principle : {Back (Residual) titration}
It depends upon the precipitation of Br- as AgBr by the addition of
a known excess of standard AgNO3 THEN the remaining unreacted AgNO3 is
back titrated against standard NH4SCN using ferric alum indicator.
1 Br- + Ag+ 
 AgBr 
(sample) (25 ml st. AgNO3) yellowish
white ppt
2 Titration reaction:
NH4SCN titrant
Ag+ + SCN- 
 AgSCN 
(remaining unused excess) (NH4SCN titrant) white ppt
3 End point reaction: remaining unused AgNO3

+ Fe3+ indicator
SCN- + Fe3+ 
 [Fe(SCN)]2+
st
(1 dr. excess after complete (indicator) faint orange
reactn with the unused Ag+) or faint red color
Bromide is determined by Volhard's method in the same way as
chloride but without removing the ppted AgBr because it is more
insoluble (lower Ksp) than AgSCN so SCN- ion will not attack
AgBr ppt after complete reaction with the unused Ag+.
Procedure for the detn. of KBr by Volhard's method :

!!! BEFORE STARTING THE DETERMINATION,
WASH ALL THE GLASSWARE WITH DISTILLED WATER.
(because tap water contains Cl – which interferes with the determination)
1 Transfer accurately 10 ml of the sample into a clean glass stoppered flask.
2 Add 2 ml conc. HNO3.
3 Add 25 ml of 0.05 N AgNO3.
63
4 Shake well for few minutes to coagulate the precipitated AgBr.
5 Add 1 ml ferric alum indicator.
6 Titrate with 0.01 N NH4SCN with strong shaking.
Color at E.P.: Faint Orange Color not disappear on strong shaking.
Calculations :
In this exp., the equivalence factor (F) can be calculated on 0.05 N AgNO3
st nd
(1 standard "25 ml") OR on 0.01 N NH4SCN (2 standard "titrant") but it is
st
preferred to be calculated on the 1 standard.
If (F) is calculated on the 1st standard (0.05 N AgNO3):
1 AgNO3 ≡ 1 KBr
standard sample
1 x M.W. of KBr x 0.05

each ml of 0.05 N AgNO3 ≡ ≡ .......... g KBr
1 x 1000
0.05 N 0.01 N 0.05 N
[25 – E.P. ( 0.01 )] x F x 1000

Concn. = 0.05 = .......... g/L
10
If (F) is calculated on the 2nd standard (0.01 N NH4SCN):

1 NH4SCN ≡ 1 KBr
standard sample
1 x M.W. of KBr x 0.01

each ml of 0.01 N NH4SCN ≡ ≡ .......... g KBr
1 x 1000
0.05 N 0.01 N 0.01 N
[25 ( 0.05 ) – E.P.] x F x 1000

Concn. = 0.01 = .......... g/L
10
64
Exp.: Determination of NaCl by Fajan's method
Principle (Theory or Mechanism of action of adsorption indicators) :
It depends on the titration of NaCl sample with standard AgNO3 using
fluorescein indicator. At the E.P., the formed AgCl ppt becomes pink.
Titration reaction: NaCl + AgNO3      AgCl  + NaNO3
fluorescein ind.
sample titrant
Before starting titration: the ions present in the solution are Na+, Cl - & In-.
Stage of A During titration B 1st drop excess of AgNO3

titration: (before E.P.) immediately after the E.P.
Ions Cl- + Na+ + In- + NO3- Ag+ + NO3- + Na+ + In-
titrant titrant from ind.
present in sample sample
from ind. titrant
1st drop xss sample
solution: (Ag+ is& precipitated
ind.
as AgCl )
after E.P. & ind.
Diagram: Na+ NO3- In-
Na+ Na+ NO3-

Ag+ Ag+ NO3- In- Ag+ Ag+ In-
Cl- Cl-
spontaneous
Cl- AgCl Cl- Ag+ AgCl Ag+ Ag+ AgCl Ag+
Na+ NO3- In-
Na+ Cl- Cl- Ag+ Ag+ Ag+ Ag+
NO3- In-
Na+ NO3- In-
Color of White ppt in Pink ppt

the ppt: green fluorescence in faint colored solution
At start of tit., Immediately after the E.P., AgNO3 is
(Cl-) ions present in present in excess so (Ag+) ions form the
excess so the 1ry 1ry ads. Layer [own ions of ppt] {Note that all
adsorption layer will (Cl -) ions from sample are already precipitated}.
Explanation:
be (Cl-) ions [own The 2ry adsorption layer of the opposite

ions of ppt] and charge will be (NO3-) BUT since
the 2ry adsorption fluorescein ions carry (-ve) charge also &
layer will be the it is more strongly adsorbed than (NO3-),
oppositely charged so fluorescein replaces (NO3-) and the 2ry
(Na+) ions [counter- layer becomes (In-) & the ppt becomes
ions]. pink due to deformation of the electronic
system of the indicator anion.
65
Notes:
1) Eosin indicator can not be used for the determination of (Cl-) because
eosin is too strongly adsorbed to the surface of the ppt and may
replace (Cl-) ions in the 1ry adsorption layer before the E.P. giving
early E.P. [stage A in the diagram]
2) Effect of pH: In Fajan's method, the pH should be adjusted to keep
the indicator dissociated.
For fluorescein indicator:
Fluorescein (In-Na+) is a sod. salt of a very weak acid and it's hydrolyzed
in water to give the parent acid (InH) which is very weak and so its
dissociation is suppressed in acidic medium due to common ion effect.
InH 
 H+ + In-
H+
So fluorescein is used in neutral or slightly alkaline medium (pH=7-10).
[Note that strong alkaline pH is prohibited in argentometric tit. because
Ag+ will be precipitated as AgOH (brown to black ppt) leading to
Consumption of the titrant & Masking of the E.P. color].
For eosin indicator:
Eosin (In-Na+) is a sod. salt of a more stronger acid and so its
dissociation is not affected in acidic medium. Therefore, eosin can be
used at pH down to 2 ( i.e. pH  2).
Procedure :
10 ml sample  dilute to 50 ml with dist. water  add 15 drops

fluorescein indicator  Titrate ≠ 0.05 N AgNO3.
At the E.P., the formed AgCl ppt becomes pin
66
Chapter IV
Complexometric
titration
67
Complexometric titration
(Complex-formation titration)
Definition of Complex-formation titration :
It is a type of titrations that depends on the formation of soluble complexes.
Introduction :
♦ Complex = Coordination compound.
♦ Complex consists of an electron donor bonded to an electron acceptor
by a coordination bond.
Donor .
coordination bond Acceptor .
(= Ligand)
(= Metal)
(= Complexing agent)
 
can donate lone pair can accept lone pair of
of electrons such as electrons in its vacant
.. .. ..
N, O & S. orbitals ...... ...... ...... .
♦ Example of Complexes:
Silver ammine complex " [Ag(NH3)2]+ " where NH3 is the donor (ligand)
while Ag+ is the acceptor (metal).
[H3N: → Ag+ ← :NH3]
68
EDTA Titrations .
 It is the most common type of complex-formation titrations.

 The main complexing agent (= ligand = donor) in these titrations is EDTA.
 Basic components in any EDTA titration:
1) Metal (acceptor)  sample .
2) EDTA (donor)  the main complexing agent.
3) Indicator (donor).
4) Buffer (to adjust pH of the medium).
1 Metal :
A very large number of metals can be determined complexometrically
such as Mg2+, Ca2+, Zn2+, Al3+………………etc.
2 EDTA : { EDTA = Ethylenediaminetetraacetic acid }
It is used as disodium salt

because the parent acid is insoluble in water while the disodium salt is soluble.
O
CH2 C O H Na+
CH2 N O
CH2 C OH
O
CH2 C O H Na+
CH2 N O
CH2 C OH
 EDTA is a hexadentate ligand [ i.e. it can bind to metal ion with

6 coordination bonds because it contains 6 ligand (donor) atoms as
shown in the structure].
N.B. Generally, multidentate ligands (i.e. bi-, tri-, hexa- …… etc) are
called "Chelating agents".
69
 EDTA can form stable 1:1 complex with many divalent, trivalent and
tetravalent metal ions (i.e. 1 mole of EDTA ≡ 1 mole of metal ion) so
EDTA is always prepared as Molar solutions.
 The parent acid of EDTA is represented as H4Y while its disodium salt
is represented as H2Y2-.
3 Indicator :
 The indicators used in complexometric titrations are metal-sensitive
indicators so these indicators are called "Metal indicators".
 The color of the free indicator must differs from the color of
the [metal-indicator] complex.
 Also, these indicators are pH-sensitive indicators BUT during
titration, we adjust pH by using a suitable buffer and so the indicators
will be affected by the metal only.
 Examples of metal indicators:
1 EBT indicator (Eriochrome Black T) 2 Murexide indicator

 It is a salt of an acid.  It is a salt of an acid.
 Its parent acid is represented as  Its parent acid is represented as
(H3In) (H5In)
 EBT ind. is represented as follows:  Murexide is represented as follows:
H2In- HIn2- In3- H4In- H3In2- H2In3-
(pH  7) (pH 7-11) (pH  11) (pH  9) (pH 9-11) (pH 11)
Red Blue orange Reddish Bluish

Violet
Violet Violet
 EBT is used at pH 10 (adjusted by  Murexide is most commonly used at

Ammonia Buffer) so the color of pH 12 (adjusted by 8% NaOH) so
the free EBT will be Blue. the color of free murexide will be
Bluish Violet.
Also, murexide is sometimes used
at pH 10 (amm. buffer) where the
color of free murexide is Violet.
 The color of [metal-EBT] complex is  The color of [metal-murexide] complex
usually Wine-red color. differs according to the metal & pH.
70
 Ex. of metals determined using EBT:  Ex. of metals determined using murexide:
Mg2+, Zn2+, Hg2+ Ca2+ (at pH 12) & Ni2+ (at pH 10).
Question: (Choose the correct answer)
EBT and murexide are (metal sensitive - pH sensitive - both)
4 Buffer :
 Role of buffer in complexometric titrations:
1) Consume the released protons from the reaction between metal and
EDTA and so make the reaction go forward.
Metal + EDTA (metal-EDTA) complex + 2H+
2) Keep pH constant and so keep the correct color of the indicator.
 Examples of buffers used:

1) Ammonia buffer (pH = 10).
2) 8% NaOH (pH = 12).
Methods of EDTA titrations

1. Direct titrations:
Direct titration of metal sample ≠ standard EDTA.
2. Back (Residual) titrations:

Metal sample + known excess of standard EDTA

Back titration of the remaining unreacted EDTA ≠ standard metal solution.
3. Replacement (Substitution) titrations:

Metal sample + (Mg-EDTA) solution  (metal-EDTA) + equivalent amount of Mg2+

Titration ≠ standard EDTA.
4. Alkalimetric titrations:
Metal sample + EDTA solution (metal-EDTA) complex + 2H+

Titration ≠ standard NaOH
5. Miscellaneous methods:
71
Ex.: Determination of Ag+ sample.
Examples of Complexometric titrations

Introduction :
General Principles for Complexometric Titrations:

 The complex is formed between Metal & EDTA or between Metal & Indicator
{Not between EDTA & Indicator because both of them are
electron- donors (ligands)}.
 (Metal-EDTA) complex must be more stable than (Metal-Indicator) complex.
 The change in color at the end point is due to change of:
[complexed ind. into free ind.]…………………………………………in direct titration

OR
[free ind. into complexed ind.]………………………………………….in back titration.
Sketch Diagrams for

Direct Complexometric Titrations  EDTA
These symbols will be used in the following diagrams:
Mg 2+
= Magnesium ion.
Murexide = Free Murexide indicator.
Ca2+ = Calcium ion. Mg 2+
= Complexed EBT indicator.

EBT
EDTA = Disodium salt of Ca2+

= Complexed Murexide ind.
ethylenediaminetetraacetic Murexide
acid.
EBT = Free EBT indicator.

72
Exp.: Complexometric Determination of MgSO4.7H2O
Principle :
Direct titration of Mg2+ with standard EDTA at pH = 10 (amm. buffer)
using EBT indicator.
Equations: (Please, Refer to previous sketch diagrams)
Before starting titration:

Mg2+ + HIn2-  MgIn- + H+
sample EBT ind. complexed EBT
(wine red)
During titration  EDTA:

Mg2+ + H2Y2-  MgY2- + 2H+
EDTA
(titrant)
Just before & at the E.P.:

MgIn- + H2Y2-  MgY2- + H+ + HIn2-
Free EBT
(blue)
(This reaction occurs because Mg-EDTA complex is more stable than Mg-EBT complex)
Procedure :
2) Add 2 ml of Amm. buffer.
3) Add few specks of EBT indicator.
4) Titrate  0.01 M EDTA.
{ Color change at E.P.: from Wine Red to Pure Blue }

Complexed Free
EBT ind. EBT ind.
75
Calculations :
Calculations in complexometric titrations differ from that in
other types of titration in the calculation of equivalence factor where
( b ) in complexometric titrations is Absent because we always use Molar
concentrations in complexometric titrations.

Mg2+ + H2Y2-  MgY2- + 2H+
sample standard
 1 EDTA ≡ 1 MgSO4.7H2O
standard sample
1 x M.W. of MgSO4.7H2O x 0.01

each ml of 0.01 M EDTA ≡ ≡..g MgSO4.7H2O
1000
Concentration:
E.P. x F x 1000
Concn. = = .......... g/L
10
76
Exp.: Complexometric Determination of CaCl2.6H2O
Principle :
Direct titration of Ca2+ with standard EDTA at pH = 12 (8% NaOH)
using murexide indicator.
Equations: (Please, Refer to previous sketch diagrams)
Before starting titration:

Ca2+ + H2In3-  CaH2In-
sample murexide complexed murexide
ind. (rose red)
During titration  EDTA:

Ca2+ + H2Y2-  CaY2- + 2H+
EDTA
(titrant)
Just before & at the E.P.:
CaH2In- + H2Y2-  CaY2- + 2H+ + H2In3-
Free murexide
(bluish violet)
(This reaction occurs because Ca-EDTA complex is more stable than Ca-murexide complex)
Procedure :
2) Add 2 ml of 8% NaOH.
3) Add few specks of murexide indicator.
{ Color change at E.P.: from Rose Red (Pink) to Bluish Violet }

Complexed Free
murexide ind. murexide ind.
Calculations :
Ca2+ + H2Y2-  CaY2- + 2H+

sample standard
(EDTA)
77
 1 EDTA ≡ 1 CaCl2.6H2O
standard sample
1 x M.W. of CaCl2.6H2O x 0.01

each ml of 0.01 M EDTA ≡ ≡..g CaCl2.6H2O
1000
Concentration:
E.P. x F x 1000
Concn. = = .......... g/L
10
Exp.: Complexometric Determination of
Potash alum { KAl(SO4)2.12H2O }
Principle : (back titration)
Al3+ salts can not be directly titrated  EDTA because (Al-EDTA) complex
is formed slowly so Al3+ salts are best determined by back titration.
Equation: Al3+ + H2Y2-  AlY- + 2H+

sample known excess (Al-EDTA)
of st. EDTA complex
then the remaining unreacted EDTA is back titrated  standard MgSO4
using EBT indicator & amm. buffer.
{ Color change at E.P.: from Blue to Wine Red }

Free Complexed
EBT ind. EBT ind.
Procedure :
2) Add 25 ml of 0.05 M EDTA.
3) Add 2 ml of amm. buffer.
4) Add few specks of EBT indicator. 78

5) Titrate  0.05 M MgSO4
{ Color change at E.P.: from Blue to Wine Red }

Free Complexed
EBT ind. EBT ind.
Calculations :
 1 EDTA ≡ 1 Al3+
standard sample
1 x M.W. of KAl(SO4)2.12H2O x 0.05 ≡………...g

each ml of 0.05 M EDTA ≡
1000 KAl(SO4)2.12H2O
Concentration:
(25 - E.P.) x F x 1000
Concn. = = .......... g/L
10
Results:
E.P. =
Concn. =
Exp.: Complexometric determination of CuSO4.6H2O

Principle:
By titration ≠ standard EDTA using PAN indicator & Acetate
buffer.
{PAN = Pyridylazonaphthol}
Color change: from Pink (complexed PAN) to Yellowish Green (free PAN).
N.B. PAN indicator allows selective titration of Cu2+ in presence
of Ba2+, Ca2+, Mg2+ & Mn2+.
Procedure:
2) Add 2 ml of acetate buffer.
3) Add 5 drops of PAN indicator.
{ Color change at E.P.: from Pink to Yellowish Green }

Complexed Free
PAN ind. PAN ind.
Calculations :
Cu2+ + H2Y2-  CuY2- + 2H+

EDTA
 1 EDTA ≡ 1 CuSO4.5H2O
standard sample
1 x M.W. of CuSO4.5H2O x 0.01 ≡..g CuSO4.5H2O
each ml of 0.01 M EDTA ≡
1000
Concentration:
E.P1 x F x 1000
Concn. of CuSO4.5H2O = = .......... g/L
10
Exp.: Complexometric Determination of (Ca2+/Mg2+) Mixture
(CaCl2.6H2O & MgSO4.7H2O)
Principle : (direct titration)

c) First step: (Determination of Ca2+only).
By titrating 10 ml of the mixture ≠ standard EDTA using
8% NaOH & murexide indicator.
E.P1 ≡ Ca2+ only.
d) Second step: (Determination of total Ca2+ & Mg2+).
By titrating another 10 ml of the mixture ≠ standard EDTA using
amm. buffer & EBT indicator.
E.P2 ≡ Total (Ca2+ & Mg2+).
Notes:
1) When we use 8% NaOH (pH=12) & murexide, we determine Ca2+ ONLY
because: Mg2+ does not form any complex with EDTA at pH=12 due to
the precipitation of Mg2+ as Mg(OH)2 which is more stable than
(Mg-EDTA) complex. IN OTHER WORDS, we can say that the selectivity
of EDTA was increased to determine Ca2+ only without interference of Mg2+.
2) Ca2+ alone can not be directly determined ≠ EDTA using EBT ind.
because: EBT gives poor E.P. with Ca2+ ( i.e. the color change at E.P. is
not sharp) and that is because the binding between Ca2+ & EBT is very weak.
3) Although EBT can not be used in direct complexometric
determination of Ca2+ alone (as mentioned before), BUT it can be used
for determination of total Ca2+ & Mg2+…………………………HOW??!!
That is because:
Before starting titration: {sample (Ca2+& Mg2+) + amm. buffer + EBT }
EBT will be complexed with Mg2+ only because (Mg-EBT) complex is
more stable than (Ca-EBT) complex which is very weak (as mentioned before).
i.e. We have { free Ca2+ + free Mg2+ + (Mg-EBT) } in the flask.
During titration, the following reactions occur:
1) EDTA + free Ca2+  (Ca-EDTA) complex.
2) EDTA + free Mg2+  (Mg-EDTA) complex.
E.P. 3) EDTA + (Mg-EBT)  (Mg-EDTA) + free EBT.
blue color
i.e. EDTA reacts first with free Ca 2+
then with free Mg2+ because
(Ca-EDTA) complex is more stable than (Mg-EDTA) complex (compare with EBT).
And finally EDTA reacts with (Mg-EBT) complex and so the color
change at E.P. will be due to Mg-reaction and that gives sharp E.P.
representing (or equivalent to) the total.
Procedure :
A Murexide reading (E.P1) : (≡ Ca2+ only)
2) Add 2 ml of 8% NaOH.
3) Add few specks of murexide indicator.
{ Color change at E.P.: from Rose Red (Pink) to Bluish Violet }
Complexed Free
murexide ind. murexide ind.
B EBT reading (E.P2) : (≡ Ca2+ + Mg2+)

2) Add 2 ml of Amm. buffer.
3) Add few specks of EBT indicator.
{ Color change at E.P.: from Wine Red to Pure Blue }
Complexed Free
EBT ind. EBT ind.
82
Calculations :
E.P1 {murexide reading} ≡ Ca2+
E.P2 {EBT reading} ≡ Ca2+ + Mg2+
 (E.P2 - E.P1) ≡ Mg2+
For Ca2+ :
Ca2+ + H2Y2-  CaY2- + 2H+
EDTA
(standard)
 1 EDTA ≡ 1 CaCl2.6H2O
standard sample
1 x M.W. of CaCl2.6H2O x 0.05
each ml of 0.05 M EDTA ≡ ≡..g CaCl2.6H2O
1000
Concentration:
E.P1 x F x 1000
Concn. of CaCl2.6H2O = = .......... g/L
10
For Mg2+ :
Mg2+ + H2Y2-  MgY2- + 2H+
EDTA
(standard)
 1 EDTA ≡ 1 MgSO4.7H2O
standard sample
1 x M.W. of MgSO4.7H2O x 0.05
each ml of 0.05 M EDTA ≡ ≡..g MgSO4.7H2O
1000
Concentration:
(E.P2 - E.P1) x F x 1000
Concn. of MgSO4.7H2O = = .......... g/L
10
Results:
E.P1 =
E.P2 =
Concn. of CaCl2.6H2O =
Concn. of MgSO4.7H2O =
Instructions for
using
the Glassware
‫األدوات المطلوبة لعملي الكيمياء التحليلية الصيدلية‬
‫و طـريقة استعمالھا‬
‫‪ (١‬الدورق المخروطي )‪) :(250 ml Conical Flask‬تدريجه غير دقيق(‬
‫} ُيغسـل بالماء فقط{‪.‬‬
‫‪ (٢‬الماصة ذات الفقاعة )"‪) :(Bulb or Transfer Pipet "Pipette‬تدريجھا دقيق ج ًدا(‬
‫مطلوب منھا ماصتين‪10 ml and 25 ml pipets :‬‬
‫ستمأل به{‪.‬‬
‫ُ‬ ‫} ُتغسل بالماء ثم بالمحلول الذي‬
‫طريقة االستخدام بالتفصيل ) ُتنفـذ بالترتيب(‬

‫‪ .١‬اغسل الماصة جي ًدا بالماء‪.‬‬
‫‪ .٢‬جفف الماصة جي ًدا من الخارج بمنديل‪.‬‬
‫‪ .٣‬اغسل الماصة جي ًدا بالمحلول الذي ستمأل به‪.‬‬
‫‪ .٤‬جفف أصابعك و جفف فوھة الماصة جي ًدا‪.‬‬
‫‪ .٥‬امأل الماصة لما بعد )أي أعلى من( عالمة الـ‪ ١٠‬مللي‪.‬‬
‫‪ .٦‬امسح الماصة جي ًدا من الخارج بمنديل‪.‬‬
‫‪ .٧‬اضبط سطح المحل ول عل ى عالم ة ال ـ‪ ١٠‬ملل ي )بتخفي ف ض غط اص بعك )ال سبابة( ت دريجيًا‪،‬‬
‫و يساعد في ذلك أن تدير الماصة بيدك اليسرى(‪.‬‬
‫ملحوظات ھامة على ھذه الخطوة‪:‬‬
‫‪ ‬مسك فوھة الماصة يكون باصبع السبابة‪.‬‬
‫‪ ‬ضبط المحلول على عالمة الـ‪ ١٠‬يكون للحد السفلي لسطح المحلول‪.‬‬
‫‪ ‬عند ضبط المحلول يجب أن تكون عالمة الـ‪ ١٠‬في نفس مستوى العين‪.‬‬
‫‪ ‬بع د م أل الماص ة ح افظ دائ ًم ا عل ى أن يك ون وض عھا رأس يًا أثن اء م سكھا ألن إمال ة‬
‫الماصة قد تسبب دخول فقاعات ھواء داخلھا‪.‬‬
‫‪ ‬احذر المشي بالماصة بعد ضبط المحلول على عالمة الـ‪.١٠‬‬
‫‪ ‬احذر مسح الماصة بمنديل بعد ضبط المحلول على عالمة الـ‪.١٠‬‬
‫‪ .٨‬تأكد من عدم وجود أي فقاعة ھواء في الماصة بعد مألھا‪ ،‬وإال تعيد مألھا مرة أخرى‪.‬‬
‫‪ .٩‬فرّغ محتويات الماصة داخل الفالسك كالتالي‪:‬‬
‫‪ ‬اجعل الفالسك مائال بزاوية ‪ °٤٥‬و الماصة رأسية‪.‬‬
‫‪ ‬اترك الماصة تفرغ محتوياتھا ثم انتظر ‪ ١٥‬ثانية على األقل و الماصة مازالت داخل الفالسك‪.‬‬
‫‪ ‬فرّغ آخر كمية في الماصة عن طريق لمس مقدمة الماصة برفق للجزء الجاف من الفالسك‪.‬‬
‫‪ ‬اعلم أن آخر نقطة بالماصة )تشغل تقريبا مسافة ‪ ٠.١‬سـم في نھاية الماص ة( غي ر مح سوبة‬
‫في حجم الماصة لذلك إنزالھا غير مطلوب‪.‬‬
‫‪ (٣‬السحاحة )"‪) :(Buret "Burette‬تدريجھا دقيق ج ًدا(‬
‫مطلوب سحاحة واحدة فقط‪25 ml OR 50 ml :‬‬
‫ستمأل به{‪.‬‬
‫ُ‬ ‫} ُتغسل بالماء ثم بالمحلول الذي‬
‫طريقة االستخدام بالتفصيل ) ُتنفـذ بالترتيب(‬

‫‪ .١‬اغسل السحاحة جي ًدا بالماء‪.‬‬
‫‪ .٢‬اغسل السحاحة جي ًدا بالمحلول الذي ستمأل به‪.‬‬
‫‪ .٣‬امأل السحاحة بالمحلول ثم قم بتفريغ فقاعات الھواء من الجزء السفلي للسحاحة‪.‬‬
‫‪ .٤‬امأل السحاحة لما بعد )أي أعلى من( عالمة الصفر‪.‬‬
‫‪ .٥‬جفف السحاحة جي ًدا من الخارج‪.‬‬
‫‪ .٦‬اض بط س طح المحل ول عل ى عالم ة ال صفر م ع مالحظ ة أن ذل ك يك ون للح د ال سفلي ل سطح‬
‫المحلول مع مراعاة أن تكون عالمة الصفر في نفس مستوى العين عند النظ ر إليھ ا‪ ،‬وينطب ق‬
‫ذلك أيضا على طريقة قراءة الـ)‪.(E.P‬‬
‫‪ .٧‬يجب مراعاة مسك السحاحة أثناء عملية الـ)‪ (Titration‬بالطريقة الموضحة‪.‬‬
‫‪ (٤‬ماصة مدرجة ‪ ١٠‬مل )"‪:(10 ml Graduated Pipet "Pipette‬‬

‫)تدريجھا غير دقيق مقار ًنة بالماصة ذات الفقاعة(‬
‫‪ (٥‬مخبار مدرج ‪ ١٠‬مل )‪:(10 ml Measuring Cylinder‬‬

‫)تدريجه غير دقيق(‬
‫‪ (٦‬بيكر ‪ ٢٥٠‬مل )‪:(250 ml Beaker‬‬

‫)تدريجه غير دقيق(‬
‫‪ (٧‬قمع زجاجي)‪.(Glass Funnel‬‬
‫‪ (٨‬حامل سحاحة )‪.(Buret Holder‬‬
‫‪.White Plate (٩‬‬
‫ﻣﻠﺤﻮﻇﺎت ﻋﺎﻣﺔ‬
‫‪ ‬احذر أن تقوم بإرجاع أي محلول إلى زجاجات المعمل بعد انتھائك من التجربة‪.‬‬
‫‪ ‬احرص على الحفاظ دائ ًما على جميع أدواتك نظيفة تما ًما بعد انتھاء المعمل‪.‬‬

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Practical

Pharmaceutical Analytical Chemistry-1

Pharmaceutical Analytical Chemistry Department

Classification of Analytical Chemistry Branches ……………..….. 5

Determination of NaCl (by Fajan’s method) 65

Chapter IV: Complexometric Titration 67

Qualitative Analysis Analysis of Anions

Acid-base titration (Aqueous & Non-aqueous)

It is a solution of known concentration & composition.

Types of standard solutions:

1. Primary Standard Solution:

♦ It is a solution whose concentration remains constant for a long

♦ It is prepared directly by dissolving known weight of the primary

standard substance in a certain volume of solvent.

2. Secondary Standard Solution:

♦ It is a solution whose concentration can be only be known

♦ The exact concentration of it is determined by a process called

♦ Standardization must be done after the preparation of

secondary standard solutions to determine their exact

concentration and correct any error if present. That is done by:-

Titrating the secondary standard solution against a primary

standard solution OR against a previously standardized

♦ Examples: NaOH and HCl.

 Remember: Solute + Solvent = Solution

1. Molarity or Molar concentration (M) :

= The number of moles of the solute per 1 liter of the solution.

N.B. Molar solution is a solution that contains 1 mole of the solute

2. Normality or Normal concentration (N) :

according to the type of the reaction. Now, it will be studied in acid-base

reactions while other reactions will be discussed later.

Definition of Equivalent Weight in acid-base reactions:

It is the weight of the substance that will release, react with or

be chemically equivalent to 1 mole of hydrogen ions (H+) in that reaction.

How to calculate it?

ex: equiv. wt. of H2SO4 = M.W. of H2SO4/2 = 98/2 = 49 g H2SO4.

ex: equiv. wt. of NaOH = M.W. of NaOH/1 = 40/1 = 40 g NaOH.

ex: equiv. wt. of CaCO3 = M.W. of CaCO3 / 2

because CaCO3 + 2 HCl CaCl2 + H2O + CO2

(i.e. 1 CaCO3 is equivalent to 2 H+).

N.B. In case of salts the number by which we divide

the M.W. of the salt is usually the sum of +ve charges on

the cation radical OR the sum of –ve charges on the anion

radical of the salt.

Equiv. wt. = M.W. of CaCO3/2 Equiv. wt. = M.W. of Na3PO4/3

Advantage of using normal concentration: Very Important

The main advantage of using normal concentration over molar ones is

facilitates our calculations.

ex. 1 L of 1 N NaOH ≡ 1 L of 1 N HCl ≡ 1 L of 1 N H2SO4 ≡ 1 L of 1 N H3PO4 ,

10 ml of 0.2 N NaOH ≡ 10 ml of 0.2 N HCl ≡ 10 ml of 0.2 N H2SO4 ≡ 10 ml of 0.2 N H3PO4

 Remember: [=] means equal while [ ≡ ] means equivalent.

 Remember: ▪ pH = - log [H+] ……………[H+] means the molar concn. of H+.

1. Methyl Orange (M.O.):

 We use 2-3 drops of it in our experiments.

 We use 10 drops of it in our experiments.

Steps for the determination of a sample

1st Preparation of the standard solution (usually HCl, H2SO4 or NaOH)

and standardization of it by titration against a primary standard

observation of the E.P.

in the flask in the burette

2- Add 10 drops ph.ph. indicator.

3- Titrate ≠ 0.1 N NaOH (in burette).

Color change at E.P.:

from Colorless to first pink persistent for 30 sec.