Documente Academic
Documente Profesional
Documente Cultură
(PC 205)
By
Staff of
Faculty of Pharmacy
Mansoura University
Contents
Subject Page
Chapter I: Introduction 4
2
Subject Page
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
Quantitative Analysis
or Determination
or Estimation
or Assay
(=How much?)
Volumetric Analysis
(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 :
period of time.
♦ Example: Na2CO3.
approximately.
"Standardization or Standardisation".
secondary standard.
--------------------------------------------------------
7
Methods of expressing the concentration of standard solutions :
The most common methods are: Molarity (M) & Normality (N).
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)
= 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
M .W . of the base
b) For bases: Equiv. wt. =
no. of replaceabl e OH in one molecule of the base
M .W . of the salt
c) For salts: Equiv. wt. =
no. of H equivalent to one molecule of the salt
9
2+ 2- 3+ 3-
CaCO3 Na3PO4
the simple 1:1 ratio involved in all reactions of the same type and that
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.
10
Chapter II
Acid-base
titration
11
Acid-Base Titrations
It's a type of titrations that involve reactions between acids and bases.
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:
2. Phenolphthalein (ph.ph.):
pH range ≈ (8.5 – 10) approximately.
Remember:
ph.ph. (small letters) is phenolphthalein indicator
while
pH (p small, H capital) is a measure of acidity or alkalinity { = –log [H+] }
2nd Titration of the sample with the prepared standard solution and
N.B. We say:
Titrate …………………… with or against or ≠ ……………………
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).
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
Vol. taken from the sample [e.g. 10 ml] ≡ (E.P.) ml of the standard
react with the sample) is added to the sample. Then after the reaction is
The amount of the first standard that reacted with the sample can be
which is equivalent to the unreacted amount of the first standard from the
15
Calculations for volumetric analysis (titration)
(x) N or (x) M
Given:
1. Volume of the sample (= 10 ml for example).
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:
≡ (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}
E.P. x F x 100
= = .......... g%
Volume taken from the sample
= .......... g/L
= .......... 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):
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
Equivalence factor (F):
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).
Principle :
NaOH + HCl
NaCl + H20
remaining standard
unreacted titrant
part
Notes:
1) Boiling is necessary for the reaction between NH4Cl and NaOH to
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:
Sample + 50 ml 1 N NaOH
50 ml of 1 N NaOH
x ml
Boil
Main experiment
part remaining
Cool
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
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
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:
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
indicator.
4 HCl + 4 NaOH
4 NaCl + 4 H2O
23
Exp.: Determination of NH4Cl & HCl mixture
Our target is to determine the concentration of each component of the mixture
Principle :
(NH4Cl does not interfere because it needs boiling to react with NaOH).
4 NH4Cl + 6 HCHO
(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
Procedure :
24
{ Color change at E.P.: from Red to Orange }
Calculations :
E.PHCl ≡ HCl only
For HCl :
HCl + NaOH
NaCl + H20
1 NaOH ≡ 1 HCl
standard sample
Concentration:
E.PHCl x F x 1000
Concn. of HCl = = .......... g/L
10
For NH4Cl :
4 NH4Cl + 6 HCHO
(CH2)6N4 + 4 HCl + 6 H20
25
4 HCl + 4 NaOH
4 NaCl + 4 H2O
1 NaOH ≡ 1 NH4Cl
standard sample
Concentration:
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)
[Theoretical] [Experimental]
- It is the point at which the added - It is the point at which the visual
It is the difference between the equivalence point and the end point.
The more accurate the titrimetric method, the smaller the titration error.
27
How to predict the shape of the titration curve?
If lower
concn.
its color.
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:
(pH = 7)
corresponds to pH=7.
7
But since the vertical part of this
29
Exp.: Determination of NaOH & Na2CO3 mixture
Principle :
Reaction equations:
For NaOH:
For Na2CO3:
Procedure :
1 E.Pph.ph. :
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--
1 HCl ≡ 1 NaOH
standard sample
Equivalence factor (F):
Concentration:
2 HCl ≡ 1 Na2CO3
standard sample
1
1 HCl ≡ Na2CO3
standard
2 sample
Concentration:
Results:
E.P1 =
E.P2 =
Concn. of NaOH =
Concn. of Na2CO3 =
32
Exp.: Determination of Na2CO3 & NaHCO3 mixture
Principle :
According to the two-indicators method:
Reaction equations:
For Na2CO3:
For NaHCO3:
N.B.:
The reaction between HCl & Na2CO3 or between HCl & NaHCO3 is
33
Procedure :
1 E.Pph.ph. :
1) Transfer 10 ml of the mixture into a clean conical flask.
2 E.PM.O. :
1) Transfer another 10 ml of the mixture into a clean conical flask.
Calculations :
1
E.P1 (ph.ph.) ≡ CO3--
2
E.P2 (M.O.) ≡ CO3-- + HCO3-
2E.P1 ≡ CO3--
2 HCl ≡ 1 Na2CO3
standard sample
1
1 HCl ≡ Na2CO3
2
standard sample
Equivalence factor (F):
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
Concentration:
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)
acetic and salicylic acids which react with sodium hydroxide giving sodium
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.
1st standard
Aspirin (sample)
NaOH + HCl
NaCl + H20
2 nd standard
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
Calculation of concentration:
E.P. =
41
Exp.: Determination of Boric acid (H3BO3)
Principle :
Notes:
1) The reaction between glycerol and boric acid may be 2:1 (as shown in
vertical part of the titration curve will be above the pH-range of M.O.
the end point will appear very rapidly due to the hydrolysis of the
Calculations :
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 :
Calculations :
Na2B4O7 + 7 H2O 2 NaOH + 4 H3BO3
2 NaOH + 2 HCl 2 NaCl + 2 H2O
titrant
Reaction equations:
Notes:
1) During the determination of HCl only (1st E.P. using M.O.): NaOH neutralizes
HCl
H+ + Cl-
CH3COOH
H+ + CH3COO-
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.
while in the detn. of Na2CO3 ≠ HCl, E.PM.O. is higher than E.Pph.ph. provided
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 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
Equivalence factor (F):
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
Equivalence factor (F):
1 x M.W. of CH3COOH x 0.1
each ml of 0.1 N NaOH ≡ ≡ ..... g CH3COOH
1 x 1000
Concentration:
Results:
E.P1 =
E.P2 =
Concn. of HCl =
Concn. of CH3COOH =
48
Chapter III
Precipitation titration
49
Precipitation Titration
Introduction :
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.
50
Mohr's Method .
51
Exp.: Determination of NaCl by Mohr's method
Principle :
It depends on the titration of NaCl sample with standard AgNO3 using
Titration reaction:
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
Notes:
3) Effect of pH: Mohr's method should be done in neutral or slightly
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 :
During tit. ≠ AgNO3: AgCl + Cl- sample + CrO4-- ind. Turbid bright
(white ppt) (colorless) (yellow color) yellow solution
Calculations :
Calculations in precipitation titration differ from that in acid-base titration in
of the standard. In other words, (b) equals the total positive charge on the
54
1 AgNO3 ≡ 1 NaCl
standard sample
Equivalence factor (F):
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 .
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.
♦ 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:
Ksp ≡ the salt is precipitated first (i.e: the salt is more insoluble or less soluble).
salts (i.e. salts in which the valence of the cation radicle the valence
{although Ksp of Ag2CrO4 is less than Ksp of AgCl but Ag2CrO4 is more
57
Important example:
So:
If a mix. of I-, Br-, SCN-, Cl- (of near concentrations) is treated with Ag+:
+ Ag+
If we have:
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
Ag+ + SCN-
AgSCN
(remaining unused excess) (NH4SCN titrant) white ppt
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.
Question: (Complete the following)
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.
Question: (Complete the following)
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.
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.
6 Mix well.
7 Filter through a dry filter paper, rejecting the first few milliliters of
the filtrate.
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):
Equivalence factor (F):
1 AgNO3 ≡ 1 NaCl
standard sample
Calculation of concentration:
0.05 N 0.01 N 0.05 N
Calculation of concentration:
0.05 N 0.01 N 0.01 N
Concn. =
62
Exp.: Determination of KBr by Volhard's method
Principle : {Back (Residual) titration}
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
SCN- + Fe3+
[Fe(SCN)]2+
st
(1 dr. excess after complete (indicator) faint orange
reactn with the unused Ag+) or faint red color
insoluble (lower Ksp) than AgSCN so SCN- ion will not attack
63
4 Shake well for few minutes to coagulate the precipitated AgBr.
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):
Equivalence factor (F):
1 AgNO3 ≡ 1 KBr
standard sample
Calculation of concentration:
0.05 N 0.01 N 0.05 N
Calculation of concentration:
0.05 N 0.01 N 0.01 N
sample titrant
Before starting titration: the ions present in the solution are Na+, Cl - & In-.
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
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
InH
H+ + In-
H+
Procedure :
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 :
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)
68
EDTA Titrations .
1 Metal :
A very large number of metals can be determined complexometrically
such as Mg2+, Ca2+, Zn2+, Al3+………………etc.
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:
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+
4. Alkalimetric titrations:
Metal sample + EDTA solution (metal-EDTA) complex + 2H+
Titration ≠ standard NaOH
5. Miscellaneous methods:
71
Ex.: Determination of Ag+ sample.
Mg 2+
= Magnesium ion.
Murexide = Free Murexide indicator.
acid.
Principle :
Direct titration of Mg2+ with standard EDTA at pH = 10 (amm. buffer)
Procedure :
75
Calculations :
1 EDTA ≡ 1 MgSO4.7H2O
standard sample
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)
Procedure :
2) Add 2 ml of 8% NaOH.
Calculations :
77
1 EDTA ≡ 1 CaCl2.6H2O
standard sample
Concentration:
E.P. x F x 1000
Concn. = = .......... g/L
10
Al3+ salts can not be directly titrated EDTA because (Al-EDTA) complex
Procedure :
Calculations :
Equivalence factor (F):
1 EDTA ≡ 1 Al3+
standard sample
Results:
E.P. =
Concn. =
Color change: from Pink (complexed PAN) to Yellowish Green (free PAN).
Procedure:
1) Transfer 10 ml of the sample into a clean conical flask.
Calculations :
1 EDTA ≡ 1 CuSO4.5H2O
standard sample
Equivalence factor (F):
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)
Procedure :
A Murexide reading (E.P1) : (≡ Ca2+ only)
1) Transfer 10 ml of the mixture into a clean conical flask.
2) Add 2 ml of 8% NaOH.
3) Add few specks of murexide indicator.
4) Titrate 0.05 M EDTA.
{ Color change at E.P.: from Rose Red (Pink) to Bluish Violet }
Complexed Free
murexide ind. murexide 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
Equivalence factor (F):
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
Equivalence factor (F):
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
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.