GHEm-t l4

DEPARTAAENT OF CH E,vIISTRY
, .{i'r ,..1
BUET, DHAKA
Course: Chem-l14
Quantitative Inorganic Analysis (Credit 3 hours/week).

PURPOSE OF CEEM.114
The main purpose of this course is to develop the basic knowledge of a student dealing with
chemical reagents. The'student will learn how to handle equipments (basic to every research
laboratory). The student will also learn techniques, how to determine the amount of a substance
quantitatively. The teacher will deliver some lectues to develop the fundamental knowledge of the
students regarding the techniques of perforrring the experiments. The skill of the students will be
developed on the basis of the to'llowing topics.

O Elementary concepts of quantitative analysis

O Chemical ssmposition of solutions: Weights and concentration units, stoichiometric relations,
problems related to these concepts.
O Intoduction to volumetric,analysis: firndamental definitions, titration cunres of acid-base and
oxidation - reduction reactions, voltrmetic calculations.
O Techniques and tools of volumetric analysis.
g Primary standard and Secondary standard substances.
O Evaluation of analytical data.
ADVICE TO TIIE STTIDENTS:
Chemisry laboratory is a place where seriousness is very much essential. Any time a
serious accident may happen due to carelessness of the shrdent. If there is an accident it \rill never
be reversible. Student will not get a second chance to recover it. Understanding of what to do, will
serve well in minimizing the danger fo-r the student. Advance preparation for the sessional class
is vety much important. To get good result in the sessional course several things a student should
to do.
Firstlyr student should understand this Laboratory manual clearly and how to use it effectively. It is
his duty to learn it carefully
Secondly, he must try to understand both the purpose and the principle behind each of the
experiment he will do.
Thirdlyr he will organize his time effectively in advance of each experiment. As in the Chemistry
Laboratory a student has to work with various hazardous chemicals, he should wear an APRON
during his sessional work.

To avoid unnecesstry hazards of explosion a sfudent should never priur any reagent
back into a stock solution bottle. If you do this then a student may inffoduce impurities which
could spoil the experiment for the person using the stock reagent after him. So pouing things back
into bottle is not only a dangerous practice but also inconsidered.

A student should not undertake any trnauthorized experiment. The chance of an accident are high
particularly with an experiment which has not been completely checked to reduce the hazard.
Because a chemistry laboratory course deals with flammable solvent at all times the danger of fire
is always present. Because of this danger DO NOT PUT INF'LAMED STICK O['MATCIDS
HERE AND TTTERE. SMOKING IN THE LABORATORY IS STRICTLY PROHIBITED.
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2 Chem-114
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. . .n.**i,dl .hr*ibals rire toriio to some exten! a studend Shoul&ineve. eat or drink in the
laboratory. There is always the possibility that whatever. a .student eats or drinks it may become
contaminated with the toxic material.

NOTE BOOK:
For recording data obtained dtring experiment: "A BOUIID I\IOTE ROOK' Should be
used. The note book should have consecutive numbered pages. If it does not, student ShoulC..
number the pages immediately. The note book is the place where all primary data must be recorded.
It is a bad practice to record primary data on loose sheet, or perishable paper. Data must be
recorded in permanent ink. Teacher may check the students note book any time. So a student
should always have it upto date. The preparation of the reports is accomplished using the material
recorded in the laboratory note book. When a student begrns the actual experiment, his note book
should always be kept nearby so that he will be able to record the data in it. Nothing should be kept
on the table, except instnrction manual, note book and calculator.
LABORATORY GLASSWARE:
Since laboratory glassware is very expensive and the person who is working with this
glassware is responsible for it, student should give proper attention and take special care of it.
Needless maltreatment of laboratory equipments may cost student in big amount of money.

Misheatment of equipment can also cause of losing time in the laboratory. A student should
be farniliar with the equipments of his experiment.

CLEANING O[' GLASSWARE:

Glassware can be cleaned more easily if it is cleaned immediately after use. It is good ,

practice to wash the equipment right away. With time the matedals left in the apparatus begin to
stick on the surface of the glass. Various washing powder and cleaning agents *uy * used as aids
T tr! washing glassware, synthetic detergents may also be used. Organi solveni may be used in
cleaning if the adhering substance is organic one. When solvents are used in cleaning glassware
caution should be taken since the solvents are hazardous. Acetone is a commonly used-solvent for
cleaning glassware, but it is expensive. Don't use reagent grade acetone for cleaning pulpose.
Waste acetone can be reused effectively several times before it is spent. For troublesome-stains and
residues which remain adhering to the glassware inspite of your best effort, a cleaning solution may
be used. The most .o--orly used cleaning solution consists of 35 mL of saturated
potassium dicromate solution dissolved in one liter concentrated sulfuric acid. A "qo.om cteaning
solution is to be prepared by dissolving sufficient dichromate in oneliter conc. sulfuric acid to
prepare a saturated solution. It is much more hazardous to add the aqueous solution to concentrated
acid since spattering may result. The preparation of cleaning solution is quite hazardous, it should
not be undertaken without careful preparation. Don't allow cleaning solution to come in contact
with your skin or your clolhing. Always use small amount of cleaning solution. Swirl the cleaning
solution in the glassware for a few minutes and pour the remaining cleaning solution into the stock
bottle. Be sure that the flask is rinsed with sufficient amount of water.

REPORT WRITING:
Students are advised to follow the following sequences in order to submit their report on the
experiment that will be carried out in this course:
I. Introduction / Objective:
Theory of the process (students should mention the name and objective of the corresponding
-typ"r
gxryrime,nt), the methods, chemical reaction(s) involved in the corresponding experimen! ol
indicators if necessary for a particular experiment should be included in this sission.
2. Name of the chemicals:
With formula used in each experiment.
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3. Experimental data:
The student should prepare a table (one must mention properly the title i.e. what one is
going to be determine. Student should also me,ntion accurately the units of its parameters and
experimental cotrditions like, whether the experiment is carried out in acidic oi b^ir media
experimental temperature etc.).

4. Calculations:
Students are advised to report their calculations in terms ofNormality as well as Molarity. It
is advisable that the students must have a proper clear concept of UMTS, specially of:.:
Units.
Concenhations i i:
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5. Results:
Briefly mention the observed value(s).
6. Percentage ofError:
o/o
One should calculate of error by using the following fomrulae:

Known value- Observe value

xtuu
7. Discussion:
Preference should be given on what sort of precautions should one take during conducting
the experiment; what are the possible erors that cause the deviation of the result from the expected
value,

MARKS DISTRIBUTION:
The performance of a student will be evaluated according to the following:
Practical Examination 40
Report 30
Viva Voce 2A
Attendance t0
Class Per{ormance 10
Quiz 40
Total Marks 150
REF. BOOKS:
1. A Text Book of Quantitative Inorganic Analysis, Dy- A.I. Vogel.
2. Practical Chemistry,6y- Mahbubul Huq and Jabbar Mian.

SOME BASIC CONCEPTS REOIIIRED F'OR THIS COI.]RSE:

For acid- base reactions:

* Definition of acid and base
+ Strength of acid and base
O Neuhalization reaction
.) The pH ofthe solution and pH scale
A Acid - base - ionization equillibrium
$Buffer solution and buffer action and their uses Henderson equations and their use
OAcid-base titration cufl/es, Acid-base indicator and their uses
4Definition oftitrant, titand, titration equivalence point, etc.
+Type of tiration
+Standard substances and standard solutions
OConcentation of solutions and their units
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+ Chem-114

For Oxidation - Reduction reactions:

+ Dofinition,of oxidization-reduction (Redox) reactions.
A Oxidation number and oxidation state.
c) Oxidizing agent/oxidant and reducing agent /reluctant.
* Oxidation nurnber.
c) Type of oxidation-reduction reactions and balancing oxidation-reduction reactions.
"} Electro-chemical cells and half- reaction.
* Potential difference and electomotive force (El"[F) and standard electrode-potentials.
c) Strength of oxidizing - reducing agents.
Q Example of some important application of redox reactions.

E)Kgf. NO.: t.
STANDARDIZATION OF NaOH SOLUTION WTH STANDARD OXALIC ACID
SOLUTION:
PRDPARATTON OF N/10 OX4,LIC ACID SOLUTION:
Transfer 0.63 g. of pure Oxalic Acid QIOOC-COOH. 21120) in a 100 mI volumetric flask and then
dissolve it with distilled water upto the mark. Normality of the prepared acid solution will be
calculated as
Wcight taken iu Efam x 0.1 N
0.63
PROCEDT'RE..
Take 10 mL of supplied NaOH solution in a conical flask by means of a pipette and dilute it to
about 50 mL. Add one drop of Phenolphthalein indicator to the solution. Then add Standard Oxalic
Acid solution drop by drop from a burette. Shake the flask frequently while adding the acid
solution. Storp the addition of oxalic acid solution as soon as the pink colour of the solution just
disappears. Note the burette reading. The burette reading should be taken carefully at the lower
meniscus of the liquid. Diff[erence of the initial and final buette reading gives the volume of the
acid added. The process should be repeated at least twice. These should agee within * 0.1 mL.
Calculate the normality of the supplied NaOH solution. Using the following relation.

Formulae = V ecid x N ectd = V b.* x N ue.c

Students shoald know:
D What is the normality of supplied solution?
Ct What are the molecular structure of phenolphthalein and oxalic acid?
D How does the indicator (phenolphthalein) work?
0 At what pH does the indicator changes its color?
tr Do you know why we see different color of different solutions?
E)rPr. NO. 2.
STANDARDIZATION OF HYDROCHLORIC ACID WITH STANDARD NaOH SOLUTION.
(a) Standardize the supplied NaOH solution as in Experiment No.l.
(b) Prenaration of aooroximatelv N/l0llvdrochloric acid (IICD solution.
Take about 1.2 - 1.3 mL conc. HCI in a 100 mL volumetric flask and add distilled water upto the
mark.

PROCEDURE:
Take 10 mL standard NaOH solution in a conical flask and dilute it to about 50 mL. Add 2 or 3
drops of Methyl Orange indicator to the solution. Then add previously prepared (approx. Nn0/ HCI
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5 Chem-114

acid solution drop wise from a burette. Shake the flask frequently druing addition of HCI acid. Stop
addition of HCI acid solution as soon as the yellow color of the solution just changes to orange.
Note the burette reading. Repeat the process at least two times and these.should agree wittlin 0.1 t
mL. Calculate the normality of the dilute HCI and from there calculate the shength of commercial
HCI.
(a) Vu.* x Nu"r. = Vdiht ..id X Sditutcacid
O) Vonrt ."io x Sau ecid dctcruinc = Vconc.rcid trken X Nconc. ecid to bc dctcrminc

StuderrB should know:

tr What is the normality of the supplied HCI solution?
O What is the molecular stnrcture of methyl orange indicator?
tr Can we use phenolphthalein instead of methyl onmge here? Justiff your answer.
O At what pH does the indicator changes its color?
tr Is it necessary to use buffer solution here? If not why?
E:rPr. Ifo.3
STANDARDIZATION OF HCI W|TH STANDARD NazGOa SOLUTTON
PREPARATION Of 0.tN NraCOs SOLUTI0N:
Transfer 0.53 g of anhydrous NazCOr in a 100 mL volumetic flask and then dissolve with distilled
water upto the mark.

PROCEDURE:
Take l0 mL of standard NazCOr solution in a conical flask and dilute it to about 50 mL. Add one
drop of phenolphthalein and titate against HCI (prepared as Expt.No.2) contained in a bureffe.
Now note the burette reading when just one drop of HCI discharges the pink color of &e solution.
This is the first end point. Then add34 drops of tut thyl Orange inside the same conical flask and
continue titration against the same HCI acid. The end point reached when the yellow colour of the
solutionjust changes to faint pink (Orange). Note the br:rette reading. This is the second end point.
The difference of the burette reading from initial to second end point will be the volume of the acid
required in the titation. Repeat the whole experiment twice and these should agree within 0.1 t
mL initial to second end point. Calculate the strength of dit. HCI acid and then find out the
nomrality of commercial conc. HCI acid.
N.B. Follow theformulae used in Expt. No. 2(a) and (b).to calculate the cane. of HCl.
Student should know:
fl Is NazCOt a primary standard substance?
D S/hy do you need to use two indicators here?
Q C* you use methyl orange first instead ofphenolphthalein? Justiry your answer.
tr can you calculate the norrrality or molarity from the half-reaction?

ErPr. NO.4
STANDARDIZATION OF SODIUM THIOSULPHATE SOLUTION WITH A STANDARD
POTASSIUM DICHROMATE SOLUTION.

LUTION:
Transfer0.49gprrreK2Cr2ozintoal00mLvolumeticnffidwithdistil1ed
water upto the mark.

PR,OCEDURE:
Take 4 mL of 10% Potassium Iodide (KI) solution in a conical flask and dilute it to about 50 mL.
Add about I g. of NaFICOg and shake the flask until the salt dissolves. Add about 4 mL. conc. HCI
 6 Chem-114

acid and then add l0 mL standard KzCrzOz solution by means of a pipette in the same flask. Shake
the flask and cover it with a watch glass, allow the solution to stand for about five minutes in the
dark (inside the desk). Rinse the watch glass and dilute the solution about 100 mL. Titrate the
liberated iodine with sodium thiosulphate solution from a burette until the brown colour fades (light
yellow). Add about I mL starch solution and continue titration by adding sodium thiosulphate
solution from the burette until one drop of the sodium thiosulfate solution changes the colour of the
solution from deep blue to light green or light blue. This is the end point. Calculate the stength of
sodium thiosulphate solution using the following equation:
V1 x51 =V2x52
Students should know:
E How does a Redox-indicator work?
Ct What is the difference between acid-base and a redox indicator?
tr Canyou identiff whether K[, KzCrzOz, NaHCOT are primary or secondary standard substance?
fl Can you use any other chemicals instead ofNaHCOl?
tr Why you should cover the conical flask after adding NaHCOI?
tr Why it is necessary to keep your experimental solution in the dark?
O Why you observe brown color for liberation of iodine instead of deep violet color?
E How do you say which q)ddizing/reducing agent stonger or weaker than other?
O What is the function of starch and why is the necessary to add starch just before the end point of
the titration?

EXPT. NO.s
ESTIMATION OF COPPER CONTAINED IN A SUPPLIED SOLUTION BY IODOMETRIC
METHOD.
N.B. Standardize Sodium thiosulphate solution as Expt.No.4.

PROCEDURE:
Pipette out 10 mL of supplied Copper salt solution into a conical flask. Add a few drop of dil.
NaOH or NaHCO3 or Na2CO3. A pale greenish precipitate should appear. Dissolve the precipitate
by adding few drop of acetic acid (CHTCOOID. Add about l0 mL of l0Yo potassium iodide (KI)
solution and titate the liberated iodine against the standard thiozulphate solution (Standardized
previously) until the brown colour of iodine changes to light yellow. Add I mL of starch solution
and continue titration till the blue colour begins to fade. Now add few drops of l0% Ammonium
thiocyanate solution and continue titration until the blue color is just discharged. Calculate the
amount of copper present in one liter of the supplied solution.

HINTS: Try to generate the following equation from which you can calculate the amount of
copper per liter.
2CuSOl=12=2N42S203
1 mI. 1N NezSzOr = 0.06354 g of Cu2*
Studen8 should know:
O What is the purpose of adding ttre NazCOi and CHI-COOH solution?
O What is the desirable pH for the reaction between Cu2" and KI?
tr What is the purpose of adding NI{4SCN solution?
E Do you know why most of the copper salts have blue color?
 7 Chem-114

E)XP[. IYO. 6 'i

DETERMINATION OF FERROUS IRON BY A STANDARD POTASSIUM OICXROITAIi.
SOLUTION.

PROCEDIIRE:
Take 10 mL of the supplied iron (Mohr's salt) solution in a conical flask. Add 50 mL 2N sulturic
acid and 5 mL of conc. Phosphoric acid. Then add 4-5 drops of diphenyl arnine indicator and titrate,
slowly against standard Potassitrrr Dichromate solution dropwise maintaining an interval of few
seconds between each drop until the addition of one drop causes the formation of intense purple or
violet blue colouration which remains permanent and is ruraffected by further addition of
t
dichromate solution, Repeat the experiment at least twice. These should agrce within 0.1 mL.
Calculate the arnount of iron per liter of solution
HINTS: Try to generate thefollowing equation to estimate iron in the supplied solution.
1 mL IN KzCrzOT = 0.05585 g Fe2*
Studen$ should know:
D Wlry it is necessary to use both the sulfuric acid as well as phosphoric acid in the experiment?
O Do you know the equation corresponding to the color changes of diphenyl amine indicator?
O What causes the intense puple or violet coloration of the experimental solution?
tr Could you use KN[nOl instead of KzCrzOz and what advantage does K2Cr2Oz has over KMnOn?
D Why the solution shows light bottle green color after addition of KzCrzOz and also after the
end point is achieved?

E:KPT. NO. 7
STANDARDIZATION OF POTASSIUM PERIUANGANATE SOLUTION wlTH
STANDARD SODIUIT/I OXALATE SOLUTION.

Preparation of standerd N/10 sodium oxalate solution:

Take 0.67 g of sodium oxalate solution in a 100 mL volumetic flask and dissolve with distilled
water upto mark.
PROCEDT]RE:
Pipette out l0 mL N/10 standard Oxalate solution in a conical flask. Add about 50 mL 2 N sulfrric
acid solution to it. Heat the solution upto 60 to 70 oC and then add 4-S drops of KMnOI solution
from a burette. Shake the solution until the colour disappears. Continue to add permanganate
solution from the burette at a moderate rate and shake the clear solution continuously. As the color
disappears more slowly, slow down the addition of permanganate solution dropwise until one drop
gives a light but permanent pink colour. This is the end point of the titration. Repeat the experiment
thrice and calculate the nonnality of pennanganate solution.

Studen$ know:
D W}ry you don't have to use any indicator in this experiment?
D Why you have to heat the experimental solution?
D Do you know about the effect produced by the change in temperature of a reaction mixttre?
D What happens if you do not shake solution properly?
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EXPr. IVO. g
DETERIIIINATION OF FERROUS ION lN A SOLUTION BY STANDARD KMnOr
SOLUTION.

N.B. Standardize Sodium Kh[nOt solution as Expt. No. 7.

PROCEDURE
Pipette out l0 rnl- of iron solution (Morh's salD in a conical flask. Add about 6 mL of 2N sulfuric
acid solution. Dilute it to about 50 mL distilled water. Titrate the resulting solution with standard
Potassiurr Pernoanganate solution. The end point is indicated by the first appearance of permanent
light pink color as in Expt. No. 7. Repeat the titation at least thrice.
Calculate the amount of iron of the supplied solution.

HINTS: Try to genetote thefollowing equafion to estimote iron in the sapptied solafion.
1 mL IN KMnO4: 0.05585 g tr'e2*
Student shows knows:
O What would happen if you use HCI or HNO3 acid instead of HzSOn?
tr What are the disadvantages of usirg KIUnOI?

E:XP[. IYO.g
Determination of total hardness by complexometric method [Using EBT (Eriochrom
Black T)l as indicator.

PROCEDURE:
Take 50 mL of sample water with a pipette in a conical flask. Add 3 mL of buffer solution
(pH=10) arrd2. 3 drops of EBT indicator. Titate the solution with standard EDTA soluiion, until
the color change from red to blue. The total hardness is expressed in parts of calcium carbonate per
million of water (ppm).

Ilints: I mL 0.01M EDTA = 1.00 mg CaCO3

End