ASSIGNMENT 4 SOLUTIONS

Q. 1 (a) Explain Mohr’s, Volhard’s, Modified Volhard and Fajan method in detail.
Include principle, detailed procedure, methodology, indicator, calculation and results.
(b) Explain quantitative estimation of sodium chloride in detail by Mohr’s, Volhard’s
and Fajan’s method.

Ans- Mohr’s method –

This method determines the chloride ion concentration of a solution by titration with silver
nitrate. As the silver nitrate solution is slowly added, a precipitate of silver chloride forms.
Ag+(aq) + Cl–(aq) → AgCl(s) The end point of the titration occurs when all the chloride ions
are precipitated. Then additional silver ions react with the chromate ions of the indicator,
potassium chromate, to form a red-brown precipitate of silver chromate.
2 Ag+(aq) + CrO 4 2– (aq) → Ag2 CrO4(s) This method can be used to determine the
chloride ion concentration of water samples from many sources such as seawater, stream
water, river water and estuary water. Seawater is used as the example here. The pH of the
sample solutions should be between 6.5 and 10. (Refer to the additional notes (3) for the
explanation). If the solutions are acidic, the gravimetric method or Volhard’s method should
be used.
Indicator used -
The Mohr method uses chromate ions (CrO42-) as the indicator for the argentometric
determination of bromide, chloride and cyanide ions. The first substance to precipitate is the
least soluble AgCl then, after the point of equivalence, the first addition to excess leads to the
precipitation of Ag2CrO4 which is brick red in colour.
Uses-
This method is used to determine the chloride concentration of water, samples from river
water and many drugs and chemical.
Mohr method
Advantage :- sample method
Disadvantage :- Alkaline solution only, Not suitable for iodide
Equipment Needed-
burette and stand
10 and 20 mL pipettes
100 mL volumetric flask
250 mL conical flasks
Solutions Needed
Silver nitrate solution: (0.1 mol L−1) If possible, dry 5 g of
AgNO3for 2 hours at 100°C and allow to cool. Accuratelyweigh about 4.25 g of solid
AgNO3and dissolve it in250 mL of distilled water in a conical flask. Store thesolution in a
brown bottle.Potassium chromate indicator solution: (approximately0.25 molL-1) Dissolve 1 g
of K2CrO4 in 20 mL distilledwater.
Determination of Chloride Ion Concentration by Titration
(Mohr’s Method)
Determination of Chloride Ion
Concentration by Titration (Mohr’s Method)
Introduction
This method determines the chloride ion concentrationof a solution by titration with silver
nitrate. As the silvernitrate solution is slowly added, a precipitate of silver chloride forms.
Ag+(aq) + Cl–(aq) → AgCl(s)
The end point of the titration occurs when all the chloride ions are precipitated. Then
additional chlorideions react with the chromate ions of the indicator,potassium chromate, to
form a red-brown precipitate ofsilver chromate.
2 Ag+(aq) + CrO42–(aq) → Ag2CrO4(s)
This method can be used to determine the chloride ionconcentration of water samples from
many sourcessuch as seawater, stream water, river water and estuarywater. Seawater is used
as the example here.The pH of the sample solutions should be between6.5 and 10. (Refer to
the additional notes (3) for theexplanation). If the solutions are acidic, the gravimetric method
or Volhard’s method should be used.
Equipment Needed-
burette and stand
10 and 20 mL pipettes
100 mL volumetric flask
250 mL conical flasks
10 mL and 100 mL measuring cylinders
Solutions Needed
Silver nitrate solution:(0.1 mol L−1) If possible, dry 5 g of
AgNO3
for 2 hours at 100°C and allow to cool. Accurately
weigh about 4.25 g of solid AgNO3
and dissolve it in 250
mL of distilled water in a conical flask. Store the solution
in a brown bottle.
Potassium chromate indicator solution: (approximately
0.25 molL-1) Dissolve 1 g of K2CrO4 dissolved in 20 mL distilled water)
Burette containing silver nitrate solution
Conical flask
Seawater and chromate
indicator
Method
Sample Preparation
If the seawater contains traces of solid matter such as
sand or seaweed, it must be filtered before use.
Titration
1. Dilute seawater by pipetting a 20 mL sample into a100 mL volumetric flask and making it
up to the mark with distilled water.
2. Pipette a 10 mL aliquot of diluted seawater into aconical flask and add about 50 mL
distilled water and1 mL of chromate indicator.
3. Titrate the sample with 0.1 mol L−1 silver nitratesolution. Although the silver chloride that
forms isa white precipitate, the chromate indicator initiallygives the cloudy solution a faint
lemon-yellow colorBefore the addition of any silver nitrate the chromateindicator gives the
clear solution a lemon-yellow colour. The endpoint of the titration is identified as the
firstappearance of a red-brown colour of silver chromate
Left flask: before the titration endpoint, addition of Ag+ions leads to formation of silver
chloride precipitate, makingthe solution cloudy. The chromate indicator gives a faint
lemonyellow colour. Centre flask: at the endpoint, all the Cl− ionshave precipitated. The
slightest excess of Ag+ precipitates withthe chromate indicator giving a slight red-brown
colouration.
Right flask: If addition of Ag+ is continued past the endpoint,further silver chromate
precipitate is formed and a strongerred-brown colour results. NB: The titration should be
stopped
when the first trace of red-brown colour is observed. Using anincompletely titrated reference
flask for comparison is a helpfulway to identify the first appearance of red-brown colouration.
4. Repeat the titration with further aliquots of diluted seawater until concordant results (titres
agreeingwithin 0.1 mL) are obtained.
Result Calculations
1. Determine the average volume of silver nitrate used from your concordant titres.
2. Calculate the moles of silver nitrate reacting.
3. Use the following reaction equation to determine the moles of chloride ions reacting.
Ag+(aq) + Cl–(aq) → AgCl(s)
4. Calculate the concentration of chloride ions in the diluted seawater.
5. Calculate the concentration of chloride ions in the original undiluted seawater.
6. Calculate the concentration of sodium chloride in the seawater in molL−1, gL−1 and g/100
mL (%).
Additional Notes
1. Residues containing silver ions are usually saved for later recovery of silver metal. Check
this with your
teacher or the laboratory supervisor.
2. The Mohr titration should be carried out under conditions of pH 6.5 – 9. At higher pH silver
ions may
be removed by precipitation with hydroxide ions, and at low pH chromate ions may be
removed by an
acid-base reaction to form hydrogen chromate ions or dichromate ions, affecting the accuracy
of the
end point.
3. It is a good idea to first carry out a “rough” titration in order to become familiar with the
colour change at
the end point.
4. The Mohr titration is sensitive to the presence of both chloride and bromide ions in solution
and will not be too accurate when there is a significant concentration of bromide present as
well as the chloride. However, in most cases, such as seawater, the bromide concentration will
be negligible. For this reason, the
method can also be used to determine either the total concentration of chloride and bromide in
solution,
or the concentration of bromide when the chloride concentration is known to be negligible.10
mL and 100 mL measuring cylinders.
Volhards method
The volhard method is a procedure for titrating silber(I) with standard potassium thiocyanate
(KSCN).
The titration is carried out in acidic solution. When the silver(I) has been precipitated as white
silver thiocyanate, the first excess of titrant and the iron(III) indicator react and form a soluble
red complex. The method is widely used for silver and chloride, because the titration can be
done in an acidic solution.
Volhard Method Procedure
The titration of silver with NH4SCN with ferric alum as an indicator is an example of the class
of titration involving the forming of a coloured substance in the solution. During titration
AgSCN is formed while at the end point excess NH4SCN reacts with Fe(III) to form deep red
[FeSCN]2+/ The amount of thiocyanate which will give a visible colour is very small. Thus,
the end point error is very small but the solution should be shaken vigorously at the end point
as silver ions are absorbed on the precipitate and are then desorbed.
In Volhards method, one can easily determine chloride ions in acidic solution, otherwise in
basic media Fe3+ will hydrolyse. An excess of AgNO3 is added to chloride solution and part of
it is unreacted. Ag solution is back titrated with ferric alum as indicator, but the method has a
source of error. AgSCN is less soluble than AgCl, So
AgCl + SCN– ⇾ AgSCN + Cl–
This will consume more NH4SCN and chloride content will appear lower. This error can be
eliminated by filtering off AgCl precipitate before back titration or if a little nitrobenzene is
added, it will adhere to AgCl and protect it from reaction with thiocyanate however,
nitrobenzene slows down the reaction.
This can be avoided if Fe(NO3)3 and a small measured amount of NH4SCN are added to the
chloride solution at the start with HNO3 and the mixture titrated with AgNO3 until the red
colour disappears.
Volhard Method in Precipitation Titration
The Volhard method is designed for the direct titration of silver in dilute nitric acid with
standard thiocyanate solution. Added ferric ion forms the clear, red colored ion FeSCN 2-, at
the precipitation endpoint.
Here, chloride can be determined indirectly by adding a known excess of standard silver
solution, then back titrating with the Volhard method. This is a less desirable approach.
However, since the ethacrynate back titrant tends to react slightly with the AgCl to form the
even more stable precipitate AgSCN.
As with the Mohr method, a blank or a titer is advised for both the direct and indirect
approaches. In the Volhard method a standard solution of thiocyanate ion (SCN) is titrated
against Ag+ using Fe3+ as the indicator.
Volhard Method Calculation
In the Volhard method silver ions are titrated with a standard solution of thiocyanate ions. The
volhard method is an indirect or back titration method in which an excess of a standard
solution of silver nitrate is added to a chloride containing sample solution.
The excess silver is then back titrated using a standardized solution of potassium or
ammonium thiocyanate with ferric ion as an indicator. The amount of silver that is
precipitated with chloride in the sample solution is calculated by subtracting the excess silver
from the original silver content.
Ag+ + Cl– ⇾ AgCl
Ag+ + SCN– ⇾ AgSCN
SCN– + Fe3+ ⇾ FeSCN
Fajans method –
Fajans method of chloride determination employs an adsorption indicator. The indicator
reaction takes place at the surface of the precipitate. The indicator is a weakly acidic dye and
exists in solution in the ionized form, In-. The titrant is a silver solution, and during the
titration a precipitate of AgCl is formed. Initially this precipitate is colloidal, consisting of
very small non-settling particles with a diameter of less than 1 µm. While this would be
undesirable for a gravimetric determination (colloids cannot be filtered), it is advantageous for
an adsorption indicator method. What happens is the following:

Precipitates have a tendency to adsorb “their own” ions to the surface to form what is known
as the primary adsorption layer, i.e., AgCl preferentially adsorbs Ag+ or Cl-, whichever
happens to be in excess. A colloidal precipitate has a very large surface area and, therefore,
presents an abundance of room for adsorption. Before the equivalence point of the titration of
Cl- with Ag+, the Cl- ion is in excess and forms the primary adsorption layer on the surface of
the AgCl precipitate. The particles have a negative surface charge and repel each other; the
colloid is stabilized by this. The indicator ion, In-, is also repelled and stays well away from
the surface. Because the particles are negatively charged, they attract cations that are in
solution more strongly than anions. Thus there is weakly bound secondary adsorption layer
consisting of the cation that forms the most insoluble chloride to AgCl (probably Na+); these
ions form the secondary adsorption layer.

Beyond the equivalence point, Ag+ is in excess and the surface of the precipitate becomes
positively charged, with the primary layer being Ag+. These positively charged colloidal
particles will now attract the indicator
-
anion
IN- and adsorb it into secondary adsorption layer.
IN
Ag+ IN-
Ag+ Ag+
+
IN-
IN - Ag
Ag+

Ag+
Ag + IN-
IN-
Ag+
Ag+ IN-
+
IN -
Ag+ Ag
The indicator forms a colored complex
IN- with silver
IN- ion, imparting a color to the precipitate.
Only at the surface is the silver ion concentration high enough for the solubility product of the
complex to be exceeded; this does not happen anywhere else in the solution, and the color is
therefore confined to the precipitate surface.
The pH must be controlled for reliable results. If it is too low, the indicator (a weak acid) is
dissociated too little to produce enough In-. In the case of Fajans method, dichlorofluorescein
is the preferred indicator and it gives good results at pH values around 7.
Since the end point does not exactly coincide with the equivalence point, the titrant should the
standardized by the same titration as used for the sample (this eliminates the inherent error).
Photodecomposition of AgCl, creating a purple-black hue on top of the white AgCl, is another
source of error. It should be minimized by carrying out the titration expeditiously and in
relative low light. As explained above, a colloidal precipitate is preferred in this titration. At
the equivalence point, neither titrant nor titrate ions are in excess, and the precipitate is
momentarily without a surface charge. This causes the colloidal particles to coagulate, thereby
reducing the precipitate surface area. It can be prevented by the addition of a small amount of
dextrin (hydrolyzed starch) to the solution.
The titration reaction is:
AgNO3 (aq) + NaCl (aq)  AgCl (s) + NaNO3 (aq)
In fact, because neither the Na+ nor NO3- ions are involved in the reaction, this reaction may
be written more accurately as:
Ag+ + Cl-  AgCl(s)
The nitrate ions are only weakly adsorbed to the precipitate after the equivalence point is
reached, and they are easily displaced by indicator ion. The end point is signaled by the
appearance of the pink color of silver dichlorofluoresceinate.
Assignment
A 0.2334-g quantity of primary standard NaCl is dissolved in 250.00 mL. A 10.00-mL aliquot
of this solution consumes 14.32 mL of a silver nitrate solution before reaching the end point in
a Fajans titration. A chloride solution, prepared by dissolving 0.2789 g of an unknown sample
in 250.00 mL and taking a 10-mL aliquot of the resulting solution, requires 11.21 mL of the
same silver nitrate solution to reach the end point. What percentage chloride (w/w) does the
unknown contain?
Apparatus
1. buret
2. 250-mL Erlenmeyer flasks
3. 10-mL pipet
 4. 250-mL volumetric flask
Chemicals
silver nitrate solution (~0.1 M)
1. sodium chloride (AR grade)
2. dextrin
3. dichlorofluorescein indicator (0.2 g in 100 mL of 3:1 ethanol:water)
4. chloride unknown
Procedure
1. The silver nitrate solution is provided in opaque plastic bottle and must be
standardized.
2. Dry about 2 g of NaCl at 120C for 1 hr. Cool in a desiccator. Prepare an ~0.10 M
NaCl standard solution by dissolving the appropriate amount of salt in a 250-mL
volumetric flask. Pipet 25.0 mL of solution into a 250-mL Erlenmeyer flask, add 5
drops of indicator, 0.05 g of dextrin, and titrate the solution in diffuse light with
constant swirling. The silver chloride flocculates shortly before the equivalence point
is reached. Carry out a rough titration quickly first of all to find approximately how
much AgNO3 is needed to reach the end point. Don’t worry if you overshoot the end
point. Then do three more replicate titrations accurately. For each the three samples,
samples add all but one milliliter of the titrant quickly while swirling the flask.
Continue the titration dropwise, again with vigorous agitation, until the precipitate
suddenly turns pink. Use the average of three results to calculate the silver nitrate
concentration.
3. Dry about 1.5 g of unknown as above. Accurately (i.e., to the nearest 0.1 mg) weigh a
~0.25-g sample by difference into a 250-mL Erlenmeyer flasks, dissolve in about 25
mL of water and titrate as above with the standardized AgNO3 solution. Accurately
weigh three more samples into Erlenmeyer flasks and dissolve each sample in ~25 mL
of water. (The flasks do not have to be dry, just clean.) Based on your first titration,
calculate how much each sample should require to reach the end point. Titrate each
sample using the same procedure as above, adding all but 1 mL of the titrant rapidly
and then approaching the end-point dropwise.
 4. For each titration, calculate the percent chloride in the unknown (to two decimal
places). Report the mean of the three determinations as your final answer. Also report
the relative standard deviation (as a percentage) of the three determinations.
Waste Disposal
Deposit all precipitates and silver waste solutions in the appropriately marked containers.

Q2.Explain the following in detail

(a)Metallochromic indicators
(b)Masking and demasking agents with case studies
(c)Standardization of Disodium EDTA
(d)Ligands and its types. Factors affecting the stability of a complex

Answer:

(a)Metallochromic indicators –
A complexometric indicator is an iono-chromic dye that undergoes a definite colour change
in presence of specific metal ions. It forms a weak complex with the ions present in the
solution, which has a significantly different colour from the form existing outside the
complex. Complexometric indicators are also known as pM indicators.
Most indicators for complexation titrations are organic dyes—known as metallochromic
indicators—that form stable complexes with metal ions.
The accuracy of an indicator’s end point depends on the relative strength of the metal–
indicator complex and the metal–EDTA complex.
If the metal–indicator complex is too strong, the change in colour occurs after the
equivalence point. If the metal–indicator complex is too weak, however, the end point occurs
before we reach the equivalence point.
Most metallochromic indicators also are weak acids. One consequence of this is that the
conditional formation constant for the metal–indicator complex depends on the titrand’s pH.
This provides some control over an indicator’s titration error because we can adjust the
strength of a metal–indicator complex by adjusted the pH at which we carry out the titration.

The common metallochromic indicators are:

1)Eriochrome Black T(EBT)/Modern Black II/ Solochrome Black T.

Eriochrome Black T is a complexometric indicator that is used in complexometric titrations,
e.g. in the water hardness determination process. It is an azo dye. EBT is blue in a buffered
solution at pH 10. It turns red when Ca2+ ions are added.
H2In- :Acidic Medium : Wine Red
HIn2- :Neutral Medium : Blue
In3- :Basic Medium: Orange
Used to determine Calcium , Magnesium , Ba , Zn, CD , Pb , Hg

2)Fast Sulphon Black F

Is a complexometric indicator used with EDTA, almost exclusively used
in copper complexation determination.
Fast Sulphon Black is purple when complexed with copper, and turns green
when titrated against EDTA,[1] as the EDTA displaces it, being the better complexing agent
due to the chelate effect.

3)Murexide
Is used in analytical chemistry as a complexometric indicator for complexometric titrations,
most often of calcium ions, but also for Cu, Ni, Co, Th and rare-earth metals. Due to the
minute amounts needed for this purpose, it is often used in a 1:250 mixture with potassium
sulfate.

H4In- :Acidic Medium : Red Violet

H3In2- :Neutral Medium : Violet
H2In4 3- :Basic Medium: Blue
Used to determine : Ca, Cu, Co
4)Pyro catechol phthalein
Has been used as a metallochromic indicator for the direct complexometric titrations of a
number of metal ions with EDTA, both in acidic and in alkaline medium. Th, Bi(III), Ba, Sr,
Ca, Mg, Mn(II), Pb(II), Cu(II), Cd, Ni, Co(II) and Zn have been successfully titrated.

5)Pyrocatechol Violet/Catechol Violet

6)Calmagite
Calmagite is a complexometric indicator used in analytical chemistry to identify the presence
of metal ions in solution. As with other metal ion indicators calmagite will change colour
when it is bound to an ion.

H2In- :Acidic Medium : Wine Red

HIn2- :Neutral Medium : Blue
In3- :Basic Medium: Orange
Used to determine: Ca, Mg , Cd

(b)Masking and demasking agents-

Masking may be defined as the process in which a substance, without physical separation of
it or its reaction products, is so transformed that it does not enter into a particular reaction.
Masking agents are additives that undergo some reaction in the sample solution that
complexes (or precipitates) potential interfering elements and converts them to a form that
does not interfere with subsequent analyte manipulation or measurement.
Masking agents are used in molecular absorption spectrophotometry, gravimetry, titrimetry,
and voltammetry.
Demasking is the process in which the masked substance regains its ability to enter into a
particular reaction.
By the use of masking agents, some of the cations in a mixture can often be 'masked' so that
they can no longer react with EDTA or with the indicator

Examples of masking agent:

(A)- KCN
It is used as masking agent for Ag+ , Cu2+ , Cd2+ , Co2+ , Ni2+ , Zn2+ , … etc.
M+ + 2 CN -  [M(CN)2] -
M+ + 4 CN -  [M(CN)4]2-
(B)- Triethanolamine : CH2CH2OH
N CH2CH2OH
CH2CH2OH
- It is used as masking agent for Fe , Al and Sn2+
3+ 3+

(C) Fluoride (e.g. NH4F):

- It is used as masking agent for Fe3+ and Al3+ to give hexafluoro complex [FeF6]3- and
[AlF6]3-
(D)- Iodide (KI):
- It is used as masking agent for Hg2+ to give tetra iodo complex (HgI4)

Demasking.-
The cyanide complexes of zinc and cadmium may be demasked with formaldehyde-acetic
acid solution or, better, with chloral hydrate : The use of masking and selective demasking
agents permits the successive titration of many metals. Thus a solution containing Mg, Zn, and
Cu can be titrated as follows:
1. Add excess of standard EDTA and back-titrate with standard Mg
solution using solochrome black as indicator. This gives the sum of al1
the metals present.
2. Treat an aliquot portion with excess of KCN (Poison !) and titrate as
before. This gives Mg only.
3. Add excess of chloral hydrate (or of formaldehyde-acetic acid solution,
to the titrated solution in order to liberate the Zn from the cyanide
complex, and titrate until the indicator turns blue. This gives the Zn only.
The Cu content may then be found by difference.
Example:
Sample: Ca + Cd + Cu
To determine concentration of each.

STEP I) Direct titration with EDTA

Ca Ca – EDTA
Cd + EDTA  Cd – EDTA ( x grams)
Cu Cu – EDTA

STEP 2) Masking Agent – KCN (Masks Cd and Cu)

Ca Ca – EDTA
Cd + EDTA (KCN) ( y grams)
Cu

STEP 3) Demasking Agent (Formal Dehydrate - HCHO)

Ca Ca – EDTA
Cd + EDTA  Cd – EDTA ( z grams)
Cu

x = Ca + Cd + Cu
y = Ca
z = Ca + Cd

 Ca = y gm
 Cu = x – z gm
 Cd = z – y gm

(c) Standardization of Disodium EDTA-

Solutions needed for this experiment- 0.01M disodium EDTA with
MgCl2 12M Hydrochloric acid Standard Ca2+ solution 8.5M NH3--‐NH4Cl Buffer Solution
of egg shells Eriochrome black T indicator.

Experimental Procedure
Preparation and standardization of 0.01 M EDTA solution.

1. Using the top loading balance, weigh between 3.6 and 3.7 grams of disodium
EDTA dihydrate into a clean 1 L plastic bottle. EDTA will leach metal ions from
soft glass containers, and should never be stored in glass containers. Add 1 L of
deionized water.

EDTA dissolves SLOWLY. Shaking or stirring the solution vigorously speeds

the dissolution process. Nevertheless, even under these conditions EDTA
dissolves SLOWLY. It is strongly recommended that the EDTA solution be
 prepared several hours or even the day before you plan on using it. Before use,
check the solution to make sure all of the solid has dissolved.

2. Using the analytical balance, weigh out ~0.1 grams of MgCl2 and add the
MgCl2 to the EDTA solution. You don’t need to wait for the EDTA to dissolve
before adding the magnesium chloride.

3. Dry about 1 gram of calcium carbonate (CaCO3) in the oven for 2 hours.
Transfer to the desiccator and cool (~ 1 hour). When cooled, weigh a
0.5-‐gram portion of calcium carbonate on the analytical balance and transfer it to
a clean 250 mL beaker.
4. Add approximately 25 mL of distilled H2O, then 5 mL of conc. HCl carefully to
the 250 mL beaker. Calcium carbonate reacts vigorously with acid, producing
carbon dioxide gas, which may spatter the beaker contents. Cover the beaker with
a watch glass. Note: If CaCO3 does not dissolve completely, add another 5 mL of
conc. HCl. When the calcium carbonate has completely dissolved, boil the
solution gently for 2-‐5 minutes, keeping the watch glass on the beaker, to expel
carbon dioxide. Analytically transfer the solution to a
500.00 mL volumetric flask and QS with DI water.

5. Pipette 25.00 mL of standard Ca2+ solution prepared in step 4 into a 250-‐mL

Erlenmeyer flask. Check the pH using pH paper: if acidic, use dilute sodium
hydroxide solution to adjust the pH to ~7. When the pH is ~ 7, add 10 mL of
8.5M NH3-‐NH4Cl buffer. This buffer has been prepared for your use.
CAUTION! This buffer is dangerous; it is caustic and ammonia can cause
pulmonary paralysis (it can interfere with your ability to breath). Exercise
caution in handling and dispensing this buffer!!

6. Add 20 mL of deionized water and 2-‐3 drops of EBT indicator. Titrate the Ca2+
standard solution with the EDTA solution until the color changes from wine red,
through purple, to a pure rich blue color. At the end point, the last traces of
purple in the solution will have just disappeared. If the reaction
 seems to proceed slowly near the equivalence point, after each addition of
EDTA wait a few seconds before adding the next drop.

Some students (not all of them male) have difficulty distinguishing between
purple and blue. You may want to make a comparison sample, representing the
endpoint of the titration. The comparison sample is made from 50 mL of DI
water, 10 mL of 8.5M NH3-‐NH4Cl buffer, and 2 – 3 drops of EBT indicator
solution. The solution should have a rich blue color and can be used for
comparison with the end point of your calcium-‐EDTA titrations.

7. Perform the titration in triplicate. Normally, three titrations will agree within
0.04 mL. Do not use all of the EDTA solution in performing the
standardization, since you must have enough EDTA to titrate the unknown
Ca2+ and eggshell solutions.

From the known mass of CaCO3, and the 1:1 stoichiometry between Ca2+ and
EDTA, you should be able to readily calculate the molarity of the EDTA
solution. Calculate the average molarity and label your EDTA solution
appropriately.

Calculations

Since EDTA forms a 1:1 complex with Ca2+ under these experimental
conditions, the millimoles of calcium present can be found by calculating the
number of millimoles of EDTA consumed during the titration using the equation

millimoles EDTA = mL EDTA X molarity EDTA

Since the total volume of the 250 ml volumetric flask has not been titrated, the
millimoles of calcium titrated (calculated from the above equation) are the millimoles
present in the aliquot titrated. A dilution factor must be used to calculate the total
number of millimoles of metal present in the 250.00 mL volumetric flask:

Total millimoles calcium = millimoles calcium X (250.00 mL/50.00 mL)

Once the total number of millimoles of calcium present in the sample is

calculated, the mass of calcium, in milligrams, is readily determined.

(d)Ligands and its types-A ligand is an ion or molecule, which donates a pair of electrons to
the central metal atom or ion to form a coordination complex. The word ligand is from Latin,
which means “tie or bind”. Ligands can be anions, cations, and neutral molecules. Ligands
act as Lewis bases (donate electron pairs) and central metal atoms viewed as Lewis acid
(electron pair acceptor). The nature of bonding between metal to ligand varies from covalent
bond to ionic bond.
Occasionally ligands can be cations (NO+, N2H5+) and electron-pair acceptors. Examples for
anionic ligands are F–, Cl–, Br–, I–, S2–, CN–, NCS–, OH–, NH2– and neutral ligands are NH3,
H2O, NO, CO.
A ligand is an ion or molecule, which binds to the central metal atom to form a coordination
entity or complex compounds. Classification of ligands is on the basis of the number of
binding sites with the central metal atom, charge and size.
Mono dentate Ligands
Monodentate ligands are also called “one-toothed“ because they bite the metal atom only in
one place .Examples-Bromide ion, Fluoride ion, Chloride ion, Iodide ion,Water
Bidentate Ligands
Lewis base which donates two lone pairs of electrons to the central metal atom is known as
bidentate ligands. They are often referred to as a “chelating ligands”. The complex which
contains chelating ligands is called “Chelates”.Examples-Acetylacetonate ion (acac),
Ethylenediammine (en), Phenanthroline (phen), Oxalate ion (ox).
Tridentate Ligands and Polydentate Ligands
Tridentate ligands have three lone pairs of electrons to the central metal atom or ion.
Molecules with four donor atoms are called tetradentate, five donor atoms are called
pentadentate and six donor atoms are called hexadentate. They are generally mentioned as
polydentate ligands.Examples-

Chelate Effect
Chelate effect explains the enhanced affinity of chelating ligands for central metal ion or
atom compared to the affinity of nonchelating monodentate ligands for the same metal.
Ambidentate ligands
Ligands with more than one potential donor atoms are known as ambidentate ligands. For
example, thiocyanate ion(NCS–) which can bind to the central metal atom or ion with either
nitrogen or sulfur atoms.
Bridging ligands
Bridging ligands is the one which is bound to more than one metal atom.

Organic ligands – A organic derivatives of above mentioned inorganic ligands and they
forms a strong bridge between metal centers.
Factors affecting the stability of a complex-
 [A]- Effect of central metal ion :
(1)- Ionic size (metal radius):
- Smaller an ion (small radius of metal)  greater its electrical field  more
stable complex
(2)- Ionic charge (metal charge):
- Metal of higher charge give more stable complexes. e.g. Ferricyanide
[hexacyanoferrate III] is more stable than Ferrocyanide [hexocyanoferrate II].
(3)- Electronegativity :
The higher acidity (electronegativity) of metal (Mn+)  the higher stability of
complex.
(4)- Metal which has incomplete outer shell (has high acidity) have more tendency to
accept electrons  more stable complex. e.g. Ca2+ , Ni2+ , Zn2+ , Mn2+ , Cu2+

Q. 3. (a) What is principle and advantages of gravimetric analysis? Describe in detail

different steps involved in gravimetric analysis.
(b) Explain Co-precipitation and post-precipitation and their different method/mechanism and
differentiate both in tabular form.

Answer:
(a)Gravimetric analysis is an unique technique by means of which either an element or a
compound is obtained in its purest form through isolation and subsequent weighing.
Example: Measuring the solids suspended in the water sample – Once a known volume of
water is filtered, the collected solids are weighed.
In order for the analysis to be accurate, certain conditions must be met:
1. The ion being analysed must be completely precipitated.
2. The precipitate must be a pure compound.
3. The precipitate must be easily filtered.

Types of Gravimetric Analysis

There are 4 fundamental types of gravimetric analysis. Of which, there are 2 common types
involving changes in the phase of the analyte to separate it from the rest of a mixture,
resulting in a change in mass.

Volatilization gravimetry
 Volatilization Gravimetry involves separating components of a mixture by heating or
chemically decomposing the sample.
Precipitation gravimetry
 Precipitation Gravimetry uses a precipitation reaction to separate one or more parts of
a solution by incorporating it into a solid.
Electrogravimetry
 Electrogravimetry is a method used to separate and quantify ions of a substance,
usually a metal.
Thermogravimetric
  Thermogravimetric is a method of thermal analysis in which changes in physical and
chemical properties of materials are measured as a function of increasing temperature
or as a function of time.

The principle of Gravimetric Analysis:

The principle behind the gravimetric analysis is that the mass of an ion in a pure compound
and can be determined. Later, used to find the mass percent of the same ion in a known
quantity of an impure compound.
Gravimetry analysis is based on the measurement of weights. First, the weight of sample
taken for analysis and second, the weight of the pure precipitate containing the constituent of
the sample that is to be determined.
aA + rR → AaRr

A = analyte, a = number of molecules of analyte reagent, R= Reagent, r = number of

molecules of reagent, AaRr = molecular formula of precipitate Here, „a‟ molecules of analyte
react completely with r molecules of reagent to produce a highly insoluble substance of
formula AaRr. This precipitate is weighed and the amount of analyte can be calculated from
their stoichiometric ratio.

The underlying principles and theories of gravimetric analysis are as below :

(i) Law of mass action and reversible reactions
(ii) Principle of solubility product
(iii) Common ion effect

Advantages of Gravimetric Analysis

If the methods are followed carefully, it provides exceedingly precise analysis. It is used to
determine the atomic masses of many elements to six-figure accuracy. It provides a little
room for instrumental error and does not require a series of standards for calculation of an
unknown.

1. It is accurate when using modern analytical balances

2. Possible sources of error are readily checked, since filtrates can be tested for completeness
of precipitate and precipitate may be examined for the presence of impurities
3. It involves direct measurement (weighing) without any calibration, thus an absolute
method
4. Inexpensive apparatus are required for determination. The most expensive requirements
being muffle furnace and in some cases, platinum crucible.
5. Under similar conditions, results are reproducible

1. Weighing of sample
2. Solution of sample
3. Precipitate formation
4. Filtration
5. Washing of precipitate
6. Digestion
7. Drying and ignition of precipitate
8. Weighing and Calculation

1. Weighing of sample
The dry sample material is weighed as required. The standard method of weighing is
to be followed.

2. Solution of sample
Most organic substances can be dissolved readily in a suitable organic solvent and
some are directly soluble in water or can be dissolved in aqueous solution of acids or
alkalis. Most inorganic substances can be dissolved in water or in dilute acids.
This may involve several steps including adjustment of the pH of the solution in order
for the precipitate to occur quantitatively and get a precipitate of desired properties,
removing interferences, adjusting the volume of the sample to suit the amount of
precipitating agent to be added

3. Precipitation
Before precipitation experiments starts the following points should be considered.
(a) Precipitation should be carried out in dilute solution considering the solubility of
precipitate, time required for filtration to minimize the co-precipitation
(b) Reagent should be mixed slowly with constant stirring so that supersaturation is
small.
(c) Precipitation is done in hot solution provided the solubility and stability of the
precipitate permits.
(d) Crystalline precipitate should be digested for a long time except in cases where
post precipitation may occur.
(e) Precipitate should be washed with appropriate dilute solution of an electrolyte,
pure water can cause peptization
(f) If precipitate is sufficiently contaminated then it should be dissolved in a suitable
solvent and re-precipitate. The precipitation method depends upon the solubility of the
product obtained from the experiment. The product must be slightly soluble. The
physical nature of the precipitates must be such that it will be readily filtered out.
Precipitation consists of two distinct events: nucleation, the initial formation of
smaller stable particles of precipitate, and particle growth. Larger particles form when
the rate of particle growth exceeds the rate of nucleation. Understanding the
 conditions favouring particle growth is important when designing a gravimetric
method of analysis. Another important factor which should be considered during
precipitation
i. Effective stirring
ii. Effective cooling
iii. Rate of addition – slow addition of the solution to make precipitate produce coarse
particle and rapid addition of generate finer particle of precipitate.

4. Filtration
It is the separation of precipitate from the mother liquor. The object is to get the
precipitate and the filtering the media quantitatively free from the solution. Apparatus
used for filtration are Simple funnel/Buchner funnel/Gooch crucible, Filtration flask,
Rubber cork, Vacuum pump, Whatman filter paper. To separate solid particulates
from their matrix, either by the gravitational force or by applying suction from a
vacuum pump or aspirator to pull the sample through a filter is employed. The type of
filter we use depends upon the size of the solid particles and the sample’s matrix.
Particle retention depends on the size of the filter’s pores. Filter paper must have
negligible ash weight. The ash of 11 cm circle should not exceed 0.0001 g. Whatman
filter papers are ashless filter papers and most suitable.

Crucibles
Crucibles serve as container for samples during thermo-analytical measurements. The
type of crucible used for a measurement can have a large effect on the quality of
results obtained. The crucible material should normally be inert i.e. it should not be
react with the sample in the temperature range used. Gooch crucibles made up of
either porcelain or silica in which ready-made, disposable, glass filter mats may use
for precipitates. But nowadays filter paper is used for this purpose as it is
advantageous sometimes. The filter paper can be burnt during the drying.

5. Washing of precipitate
The aim of washing process is to remove one or more soluble compounds as well as
surface impurities. The composition of washing solution depends on the solubility and
chemical nature of the precipitate. Pure water causes peptization and hence can’t be
used. An electrolyte solution the common ion should be utilized. It should be volatile
and should not interfere with weight. Three types of washing solutions
A. Solution which prevent the precipitate from becoming colloidal and passing
through the filter. Ammonia salts are widely used.
B. Solution which reduce the solubility of the precipitate. The wash solution may
contain a moderate concentration of a compound with one ion in common with
precipitate.
C. Solution which prevent the hydrolysis of salts of weak acids and bases.

It is crucial to wash the precipitate very well in order to remove all adsorbed species
which will add to weight of precipitate. One should be careful not to use too much
water since part of the precipitate may be lost. Also, in case of colloidal precipitates
we should not use water as a washing solution since peptization would occur. In such
situations dilute nitric acid, ammonium nitrate, or dilute acetic acid may be used.
 Usually, it is a good practice to check for the presence of precipitating agent in the
filtrate of the final washing solution. The presence of precipitating agent means that
extra washing is required. Filtration should be done in an appropriate sized ignition
filter paper.

6. Digestion
It is performed by allowing the precipitate formed to stand for 12-24 hours at room
temperature, or by warming the precipitate for some time in contact with the mother
liquor. It is also called the ageing of the precipitate. This process is advantageous as the
co-precipitation of minute particles can be eliminated and the shape of particle will tend
to more regular and denser.

7. Drying or ignition of the precipitate

Below 250 ^0C it is termed as drying and above it is ignition, to the maximum value
of 1200oC. Precipitate is dried and collected on a filter paper or in a sintered glass
crucible. For ignition silica crucible is preferred. The 4 filter paper containing
precipitate is carefully ignited to burn the filter paper as well as dried till the
precipitate weight is constant. Factors which may affect the results are heating rate,
furnace atmosphere, crucible geometry and precipitate characteristics.
Thermogravimetric methods are also employed in drying and ignition of precipitate.
In these methods, the temperature of a substance is gradually increased and its weight
is recorded at different temperature. Basically it is the drying process to attain its pure
form.

8. Weighing and Calculation

Sophisticated balances (Digital) should be used to weigh the ash/ sample. Then the
weight of substance sought can be calculated using the following formula
[weight of precipitate × (Formula weight of substance sought/Formula weight of
substance weighed)]

(b)
CO – PRECIPITATION:
During the precipitation procedure there is always chance of contamination. The
contamination of the precipitate by substances which are normally soluble in the
mother liquor is termed co-precipitation. Coprecipitated impurities may cause either
negative or positive errors.
Four important types of co-precipitation are:
1.Surface adsorption
2.Mixed-crystal formation
3.Occlusion
4.Mechanical entrapment

SURFACE ADSORPTION
The impurity is chemically or physically adsorbed onto the surface of precipitates
Adsorption is the major source of contamination in coagulated colloids but of no
significance in crystalline precipitates. Minimizing Adsorbed Impurities on Colloids
Washing a coagulated colloid with a solution containing a volatile electrolyte
Digestion: during this process, water is expelled from the solid to give a denser mass
that has a smaller specific surface area for adsorption. Reprecipitation: In this process,
the filtered solid is redissolved and reprecipitated. The solution containing the
redissolved precipitate has a significantly lower contaminant concentration than the
original, and even less adsorption occurs during the second precipitation.

MIXED CRYSTAL FORMATION:

A type of coprecipitation in which a contaminant ion replaces an ion in the lattice of a
crystal.
Ex. SrSO4 in BaSO4 , MgKPO4 in MgNH4PO4 , MnS in CdS
Mixed-crystal formation may occur in both colloidal and crystalline precipitates.

OCCLUSION:
A type of co-precipitation in which a compound (foreign ions in the counter-ion layer
) is physically trapped within a precipitate during rapid precipitate formation.

MECHANICAL ENTRAPMENT:
(a) The process of random incorporation of comparatively small quantities of other
phases (e.g., water, dust, particles, etc.) in the bulk of a precipitate during its
formation.
(b) The deliberate capture of small quantities of such phases by the deliberate addition
of solids to a liquid phase. (The term inclusion is not recommended.)

POSTPRECIPITATION:
The subsequent precipitation of a chemically different species upon the surface of an
initial precipitate usually, but not necessarily, including a common ion.
Q4) answers
a) Adsorption Indicators are substances that indicate an excess of a reactant in argentometric
titrations.
The phenomenon of adsorption is used to detect the endpoints of precipitation titrations. In
such titrations, dyestuffs like eosin, fluorescein, alizarin red etc, are used as adsorption
indicators. At the endpoint of the titration anions of indicator adsorb on precipitate and colour
change of the precipitate takes place.
For example:
When a known volume of KBr (in a conical flask) is titrated against AgNO3 (in burette)
using eosin as adsorption indicator, AgBr a white precipitate is formed.
Ag Br+ KNO3 -> AgNO3 +KBr

In the Fajans method (named after Kazimierz Fajans) typically dichlorofluorescein is used as
an indicator. The end-point is marked by the green suspension turning pink. Before the end-
point of the titration, chloride ions remain in excess. They adsorb on the AgCl surface,
imparting a negative charge to the particles. Past the equivalence point, excess silver(I) ions
adsorb on the AgCl surface, imparting a positive charge.
b) Solubility is defined as the maximum amount of a substance that will dissolve in a given
amount of solvent at a specified temperature.

The solubility product constant, Ksp , is the equilibrium constant for a solid substance
dissolving in an aqueous solution. It represents the level at which a solute dissolves in
solution. The more soluble a substance is, the higher the Ksp value it has. It is can be
represented as:

Also, there are various factors affecting the Solubility the precipitate. These are listed as
follows:
Temperature
Basically, solubility increases with temperature. It is the case for most of the solvents. The
situation is though different for gases. With increase of the temperature they became less
soluble in each other and in water, but more soluble in organic solvents.

Polarity
In most cases solutes dissolve in solvents that have a similar polarity. Chemists use a popular
aphorism to describe this feature of solutes and solvents: "Like dissolves like". Non-polar
solutes do not dissolve in polar solvents and the other way round.

Pressure
Solid and liquid solutes
For majority of solid and liquid solutes, pressure does not affect solubility.

Gas solutes
As for gasses the Henry's law states that solubility of gas is directly proportional to the
pressure of this gas. This is mathematically presented as: p = kc, where k is a temperature
dependent constant for a gas. A good proof of Henry's law can be observed when opening a
bottle of carbonated drink. When we decrease the pressure in a bottle, the gas that was
dissolved in the drink bubbles out of it.

Molecular size
The larger the molecules of the solute are, the larger is their molecular weight and their size.
It is more difficult for solvent molecules to surround bigger molecules.

If all of the above mentioned factors excluded, a general rule can be found that larger
particles are generally less soluble. If the pressure, and temperature are the same then out of
two solutes of the same polarity, the one with smaller particles is usually more soluble.

d) Gravimetric analysis is one of the most accurate and precise method of macro quantitative
analysis.
Advantages of gravimetric analysis:

1.It is accurate and precise when using modern analytical balance.

2. Possible sources of error are readily checked since filtrates can be tested for completeness
of precipitation and precipitates may be examined for the presence of impurities.

3. It is an absolute method; it involves direct measurement without any form of calibration

being required.

4. Determination can be carried out with relatively inexpensive apparatus; the most expensive
items are a muffle furnace and sometimes platinum crucibles.

5.Gravimetric analysis was used to determine the atomic masses of many elements to six
figure accuracy.

6. Gravimetry provides very little room for instrumental error and does not require a series of
standards for calculation of an unknown.

Disadvantage of Gravimetric method:

1.The main demerit is that it requires meticulous time consuming.

2.The chemist often prefers modern instrumental methods when they can be used.

3. Gravimetric analysis usually only provides for the analysis of a single element, or a limited
group of elements, at a time.

4. Methods are often complex and a slight mis-step in a procedure can often lead to unwanted
deviations.

d) Types of complexometric titration:

Direct titration
In this case, the metal ion is titrated with a standard solution of EDTA. The solution
containing the metal ion is buffered to an appropriate pH at which the stability constant of the
metal-EDTA complex is large. The free indicator has a different colour from that of the
metal-indicator complex.

Back titration
In certain circumstances a particular metal ion cannot be titrated directly. This includes
situations where:
The metal ion precipitates in the absence of EDTA.
The metal ion reacts too slowly with EDTA.
The metal ion forms an inert complex.
No suitable indicator is available.
In these cases a back titration is required. This involves addition of a known excess of EDTA
to the metal ion (buffered to an appropriate pH). Then, the excess EDT A is titrated with a
standard solution of a different metal ion. The choice of a second metal ion is important as it
must not displace the analyte metal ion from its EDTA complex.

Displacement Titration
The metal to be analyzed is added to metal-EDTA complex. The analyte ion (with higher
Kf’) displaces from the metal and the metal is subsequently titrated with standard EDTA.

Indirect Titration
The anion is first precipitated with a metal cation and the precipitate is washed and boiled
with an excess of disodium EDTA solution to form the metal complex.

e) Precipitation titration is a titration method based on the formation of precipitate,

which is slightly soluble.

The basic requirements are: The reaction must be sufficiently rapid and complete, lead
to a product of reproducible composition and of low solubility. And a method must exist
to locate the end point.

Some disadvantages are:

Slow.
Involving periods of digestion, cooling, filtration etc.
Limit the reactions that are available for titration.