LABORATORY MANUAL

For
B.Tech IYear Course CY A02

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DEPARTMENT OF CH EMISTRY
INDIAN INSTITUTE OF TECHNOLOGY ROORKEE

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[Coordinator - Prof. R.N.Goyal]

Safetv in Chemistrv Lab

[All students should read this carefully before they begin any experiment]

The chemistn'' labc'ato11'can 3e a place of discovery and learning. However, by the

very nature of ;boraic-v' ,',o.( : can be a place of danger if proper common-sense
precautions are. i ::<e' ",', - : e ,3.:' effon has been made to eliminate the use of
explosive, f'lgn,, :ci : :-c :3r: -.3.r c s;bstances from the experiments which you will
perform, there ,s a aer':a,. -.2vC 333 e 'azard assoclated with the use of a variety of
chemicals lsucn as ac,ds, a ra et: e.i q ass,,,,,are. \'ou are expected to learn and adhere to
the following general safety gu de ines icr ersu.e a safe aboratory environment for both
yourself and the people you may be wor<ing rear. Students rvho fail to follow all safety
rules may be asked to leave the Iab or suffer grading penalttes

Attire

L. Contact lenses are not allowed. Even when worn under safety goggles, various fumes
may accumulate under the lens and cause serious injuries or blindness.
2. Closed toe shoes and long pants must be worn in the lab. Sandals and shorts are not
allowed.
3. Long hair must be tied back when using open flames.

Conduct

4. No unauthorized experiments are to be performed. lf you are curious about trying a

procedure not covered in the experimental procedure, consult with your laboratory
instructor.
5. Never taste anything. Never directly smell the source of any vapor or gas; instead by
means of your cupped hand, waft a small sample to your nose. Do not inhale these
vapors but take in only enough to detect an odor if one exists.
6. Coats, backpacks, etc,, should not be left on the lab benches and stools. There is a rack
along the wall at either end of the lab, Beware that lab chemicals can destroy personal
possessions.
7. Always wash your hands very well before leaving lab.
8. Notify the teacher immediately in case of an accident.

Proper Handling of Chemicals and Equipment

9, Consider all chemicals to be hazardous unless you are instructed otherwise.

10. Know what chemicals you are using. Carefully read the labeltwicebefore taking
anything from a bottle.
 LL. use pipette carefully. Make sure that tip is dipped in
the solution. lf you accidently
suck the solution in the mouth, use lot of water
to clean it.
12. Excess reagents are never to be returned to
stock bottles. lf you take too much,
dispose of the excess.
13. Many common reagents, for example, alcohols and acetone,
are!@ily ffarnmable. Do
not use them anynrhere near open flames.
L4. Always pour acids into water nor water into acids. lf you pour.
water lmto a€id. t]ie
heat of reaction wiil cause the water to exprode into steam,
sometirnes viloilemdy, and
the acid will splatter.
L5' lf chemicals come into contact with your skin or eyes, flush immediate{yuith
coprirous
amounts of water and consult with teacher in laboratory.
16' Never point a test tube or any vessel that you are heating
at yourself or your neighbtr-
-it may erupt like a geyser.
t7 ' Dispose of chemicals properly. waste containers are provided
in the laboratory. Never
put paper, glass and similar objects in the sink, it may get
clogged. Unless you are
explicitly told otherwise, assume that only water may be put
in ttre la5 sinks.
18' clean up all broken glassware immediately and dispose of
the broken glass properfu.
19. Contact the lab attendant for any special clean_up.
20' Never leave burners unattended. Turn them off whenever you leave the class. g"
that the gas is shut off at the bench rack when you leave the lab.
ir'r.
21. Beware of hot glass--it looks exactly like cold glass.
22' Return weighing tube, bottles to the lab attendant before
leaving the lab. "i

IMPORTANT

Always write the observations in the note book and carefully

note down the number of
bottle of unknown solution.
General Guide Lines

L. Preparation of standard solution:

The proper handling of the chemlcalielectronic balance and the volumetric flask must be
learned. Let us say that ,,,,,e ,',a.: :c .',e gi'r oli a known quantity of a solid 'A'and dissolve it
in water and make -p 1:: - :'s: ,:,c', Coliect the weighing bottle from the laboratory
assistan:, Ta<: lll - ,: --::': = =).( a-C funne sr-lpplied to you, place the funnel in the
n'ro-:' :':^:'=s. a-: :a{3:.e ,,,-: e assen ll!,to the weighing room.
D ace approxirnately t[]e recu red q-a-: i]' of a s-bsrance'A in the weighing bottle, and
weigh it on the electronic balance. Note the'weight of oottie and contents (say X g)

Now take the bottle out, and tap out its contents into the funnel. Do not worry about
the crystals that stick to the sides of the bottle, weigh it again (say Y g), Then X - Y gives
the weight of substance transferred,
Using a wash bottle, wash down the contents of the funnel into the flask, ensuring that
no splashing occur from the funnel surface.
Wash the funnel repeatedly all round by giving it a circular motion while using the wash
bottle. ,

lmportant: Electronic balance should be handled very carefully and no chemical should be
spilled in the pan. Remove the substance form pan and nearby surface, if spilled by
chance.

2. Volumetric Analysis:

ln volumetric analysis, we compare the strength of two solutions by finding the volume
of one that exactly reacts with a known volume of the other. To determine the strength of
one of the solutions, the other solution of known strength is required. We call such a
solution as 'standard solution'. The act of determining the strength of the solution is called
standardization. To standardize a solution volumetrically, a solution whose strength is
known, independent of titration, is requIred. A substance whose standard solution may be
prepared without standardization by titrimetry is called primary standard.

For usefulness, a primary standard must not change its strength under storage. Sodium
hydroxide is a common chemical which can not be used as a primary standard because (i)
both, the solid and its solution absorb COz from the atmosphere, and (ii) the solution tends
to dissolve silica from glassware, used for storage. Hydrochloric acid on the other hand, can
be used as a primary standard; the so called constant - boiling hydrochloric acid. Commonly,
primary standard solutions are prepared by dissolving known weights of pure solids
(Analytical grade) reagent and making the solution up to a known volume.

Caution: Take care that the contents of the flask do not come above half the bulb of the
flask.

. Remove the funnel and swirl the flask till all the crystals are dissolved. Add distilled
water till the level reaches the neck (but below the mark) and swirl to ensure mixing.
Now raise the flask till the mark is at eye-level, and add water in drops till the lower
meniscus reached the mark. stopper the flask and shake thoroughly.
You have 100 mL of a standard solution of 'A'.

3. Handling of pipette and burette

to contain a known volume of liquid, whereas, the

The volumetric flask is designed
pipette and burette are designed to deliver B kper,,,,i vol;me at a ternperatur-e that is
marked on the bulb of the pipette or near the top of the b;retie, They deiiver the correct
volume of liquid only when the correct technique is used,

The burette should not be drained fast. All reading must be taken with the burett6
strictly vertical, and the meniscus at eye-level. For colourless solutions the lower meniscus
is read and for intensely coloured solutions read the upper meniscus. Before use, the
burette is cleaned and rinsed with the solution to be used. The solution is run off fast till
any air bubble at the tip is removed, and the stop-cock closed. lf a funnel has been used to
pour the solution into the burette it, is taken off and the burette is clarnped vertically after
noting the initial reading.

The pipette should also be washed, and rinsed with the solution to be used. To pipette
out the marked volume (say 10 mL) of solution, we suck up the liquid to a level above the
mark, and close the end with the forefinger. The vessel containing the solution and the
pipette are raised till the mark comes to eye-level, and slowly the liquid is run off till the
lower meniscus at the mark. Then the pipette tip is touched to the side of the vessel, to
remove any hanging drop, and the pipette introduced into the receiving vessel' (conical
flask)' Remove the finger from the top and run off the liquid; after the drainage is over, wait
for a few seconds and touch the tip of the pipette to the side of the vessel again, and
remove it. The drop that remains in the tip is supposed to remain there; do not blow it out
into the vessel.
 lf you perform any titration, enter the particulars neatly in a table. The reagents
involved, indicator used etc. must be clearly indicated. The titrations are to be repeated to
concordance, i.e., tilltwo consecutive titres agree.

The observations of a typicaltitration may be tabulated as given in the following example:

Trffiiom of ilaOH vs HO (shndard), tndicator: phenolphthatein

Vofrlrne of Burette readings Volume of HCI used

Triat standard or
( intermed iate solution ) (mL)
t{o- unkxlsn
(mLl

lnitial Final

L 10 0.2 10.8 10.6

2 10 10.8 2L.3 10.5

3 10 21.4 31.9 10.5

Titre value = 10.5, being concordant

Calculation: A model calculation is shown below:

I lntermediate Standard

NrVr = NzVz

N "V"
Nr
vl

ll Unknown lntermediate

N:Vs = N+ V+

NuVo
Ng
v3

Normality is multiplied with equivalent wt to get strength is gm/1.

List of experiments for course CY 002

1. Determination of sodium carbonate in washing soda.

2. Determination of Zn by EDTA (complexometric titration).
3. Wittig olefination of aldehyde or ketone lsolvent free synthesis]
4. Determination of the equivalent weight of an organic acid
5. ldentification of functional groups in an organic compound
6. Characterization of an organic/inorganic compound by UV-Vis and lR spectra
7. Synthesis of a polymer
8. Spectrophotometric determination of I*"*and concentration of KMnO+/KzCrzOzr.
9. Determination of ligand filed strength of ligands
10. Synthesis of potassium tris-oxalatochromate(lll) trihydrate.
Ll. Preparation of p-nitroacetanilide and determination of its melting point.
12. Test of carbohydrate as osazone
13. Determination of calcium in chalk/tooth paste using EDTA
14. Dye preparation
EXPERIMEHT NO. 1: Determination of sodium carbonate in washing soda.

Theory:

Anhydrous sodium carbonate reacts with standard hydrochloric acid in accordance with the
following reaction:

NazCOE +2N-lCl ) 2NaCl +HzO + COzf

The completion of the reaction is indicated by the indicator - methyl orange, which changes
from yellow colour (alkaline medium)to light pink (slightly acidic medium).

Procedure:

Prepare L00 mL of a standard solution of NazB+Oz.10H2O (approximately N/20) by weighing

accurately about 1.0 g of borax (NazBaOz.10HzO, Eq. Wt. 192.721, dissolve it in distilled
water and make up to 100 mL. Calculate its normality from the weight of borax taken.
Titrate 10 mL of this solution against the supplied hydrochloric acid (taken in burette) till
concordant titres are obtained, using 2-3 drops of methyl orange as indicator. h

a Calculate the normality of the standardized HCI solution.

a Titrate 10 mL of the given unknown solution of washing soda against the standardized
hydrochloric acid till concordant titres are obtained, using 2-3 drops of methyl orange as
indicator.
. Calculate the normality of the unknown solution and calculate the strength of NazCOr!fu

Answer the following questions:

1. Write structures of phenolphthalein and methyl orange indicators.

2. What is the structural basis of the colour change in the indicator used in this study?
3. Why does phenolphthalein change colour around pH 9.0 but the methyl orange around pH
5.0?

EXPERIMENT NO. 2: Determination of Zn by EDTA {complexometric titration)

Theory:

ln acid-base titrations the end point is generally detected by a pH-sensitive indicator. ln the
complexometric-EDTA titration a metal-ion-sensitive indicator, metal ion indicator, is often
employed to detect changes of pM. Such indicators (certain dyestuffs having resonance and
possess chelate grouping, e.g. Eriochrome black-T (EBT)) form complexes with specific metal
ions, which differ in color from the free indicator and produce a sudden color change at the
equivalence point. The metal-indicator complex must, however, be less stable than the metal-
EDTA complex to ensure that, at end point, EDTA removes metal ions from the metal-indicator
complex, and the change in equilibrium from the metal-indicator to the metal-EDTA complex
should be rapid and sharp. Zinc may be determined by complexometric titration with disodium
salt of ethylenediamine tetraacetic acid (EDTA), which forms L:1 complex with most metal ions,
using Eriochrome black-T (EBT) as indicator. The reactions involved are:

Znz* + H2Y2- <+ ZnY2-+ZH*

ZnD (red) + H2Y2- = ZnYz- + HD2- (blue) + H*

The indicator forms complex with Zn2*, the Zn-indicator complex being wine-red and the free
indicator is blue in colour. The Zn-EDTA complex is more stable than the Zn-indicator complex.
As EDTA is added to the buffered (pH = 10) solution of Zn salt in presence of Eriochrome black-
T, the EDTA reacts with free Zn2* ions, and at end point it reacts with Zn-indicator complex
liberating free indicator. The end point is a sharp colour change from wine red to blue.

Procedure:

. Prepare O.O1 M solution of zinc sulphate as a standard into the 100 mL volumetric flask in
deionized water with 1 mL of dil. HCl. Make up to the mark with deionized water'
o pipette out 10 mL of the solution into a clean conical flask and add about 2 mL of dilute
ammonia solution, 5 mL of ammonia/ammonium chloride buffer solution and 2-3 drops of
indicator. Titrate it against the EDTA solution supplied, till the colour changes from wine-red
to blue.
o pipette out 10 mL of the unknown solution into a clean conical flask and titrate it as done in
previous step.
. Report the strength of ZnSOa.THzO in g / litre.

Answer the following questions:

'J.. Give IUPAC name and structure of the indicator used. What kind of indicator this is?
2. Why do you use the di-sodium salt of EDTA but not its tetra-sodium salt?
3. What is the role of buffer solution in this experiment?
EXPERIMENT NO. 3: Wittig olefination of aldehyde or ketone [Solvent free synthesis]

Theory:

s 3^e 3':^e lr,ponant methods for the synthesis of alkenes from

: -i:: : ::-3:-, ::n',cound as an electrophile, which is attacked by a
,', ir i':=a:^: i :,D ca so,rentless Wittig reaction is shown below.

Wittig reaction is normallycarried out in two steps. ln the first step the phosphonium salt often
called as "Wittig reagent" or "Wittig salt" is treated with the base to produce the ylide. An ylide
is a species having adjacent atoms oppositely charged. ln the second step, ylide is treated with
the carbonyl compound to generate the desired alkene after the elimination of the
corresponding phosphine oxide.

ln this experiment, cinnamaldehyde is used as a carbonyl compound and

benzyltriphenylphosphonium chloride as a Wittig salt.

Procedure

ln a mortar, mix cinnamaldehyde (1.32 g), benzyltriphenylphosphonium chloride (3.9 g) and

kPO4(2.2 g) thoroughly and grind for 20 min using pestle. After every two minutes, direct the
mass into the center of the mortar using spatula. After 20 minutes, add a few milliliters of de-
ionized water to the material in the mortar. Scrape the mortar and pestle a final time to loosen
the entire product form the mortar. Filter the product using a suitable filter funnel. Discard the
filtrate that contains potassium phosphate and some triphenylphosphine oxide. Dry the off-
white solid by pressing between the filter papers, Weigh the crude product, calculate the crude
yield and record its melting point. Purify it by crystallization from absolute alcohol in a test
tube. Record the yield and melting point for the pure compound also.

Questions

L. List the other methods available for the synthesis of alkenes from alcohols, alkyl halides and
carbonyl compounds.
2. Write the mechanism of Wittig reaction.
3. Draw the structure of the other isomer of 1,4-diphenyl-L,3-butadine. Why it is not produced
in this reaction?
4. How can you prepare trons-stilbene using the Wittig reaction?
9
 EXPERIMENT No. 4: Determination of the
equivalent weight of an organic acid

Theory

Equivalent weight of an organic acid can be calculated

if normality of the acid (determined with
the help of standard organic acid say oxatic acid of known
normatity) and strength are known.
Equivalent weight = strength + normality

Procedure:

(i) Prepare a standard (approximately N/30) solution

of oxalic acid by weighing abouf'O.2 g of
crystalline oxalic acid and dissolving and making up
to 100 mL with distilled water. Titrate it
against the supplied NaoH solution from burette,
using phenolphthalein as indicator. The end
point is the appearance of faint permanent pink colour.
calculate the normality of the NaoH
solution. (NaOH is the intermediate solution).

(ii) Prepare 100 mL of solution of the given acid (about2

gof acid per litre, exactly weighed)
and determine its normality by titrimetry as above. From
the known weight of acid / litre anu
the normality determined experimentally, calculate the equivalent
weight using above formula.
Answer the fotlowing questions \..

L. How do you choose a suitabte indicator for an acid

base combination?
2. How is the equivalent weight different from molecular
mass/charge ratio?
3' How do you calculate equivalent weights of an acid,
base, oxidant and a reducing agent? '{

EXPERIMENT No- 5: ldentification of functional groups

in an organic compound

1" Test of Aromatic nature: lgnite a small amount of the given

substance, placing it on the top
of a spatula. Aromatic compound bums with a sooty frame.
2' Test of solubility: Place a pinch of the substance in a test
tube, add about 5 mL of water and
shake. lf it does not dissolve, warm the tube.

lf the substance is soluble in water, test the acidic and basic reactions
by spotting on
litmus paper' lf the substance is insoluble in water, test
solubility in dil HCl, ahd dil NaoH. Acidic
compounds dissolve in alkali, whereas basic compounds
dissolve in acid. After determining the
substance whether acidic, basic or neutral proceed to
test only for the approprirt" grorplth"
compound rnay have more than one functional groups.
Acidic functional group present: Basic functional group Neutral Functiona! Group present:
(-COOH or phenolic group or both group present: (Ketones, aldehydes, amides etc.)
oresent tooether) {-NH")
(1) Test for -COOH: Take 't mL of saturated lf the substance is (1) Test for >CO group:
solution of NaHCOs in a test tube and add a aromatic as well, a test for
pinch of the unknown to it. Vigorous primary aromatic amines Dissolve 0.1 g of the substance in
effervescence with evolution of COz confirms may be done. ethanol. Take about 5 mL
of 2,4-dinitrophenol hydrazine
COOH group.
(Diazo test): Dissolve a reagent in a test tube. Warm
slightly and add the solution to
(2) Test for phenols: pinch of substance in HCI
the reagent, and stir. A yellow to
cool and add a freshly orange precipitate is formed by
(a) To a solution of small quantity of the prepared NaNOz solution ketones and aldehydes.
given substance in watel or to crystal of
to this with cooling under
the solid add few drops of neutral ferric
chloride solution (prepare neutral ferric
tap or in ice). Add to this (2) Test for -CHO group: lf
chloride by adding dil NH4OH to FeClg an alkaline solution ol B-
naphthol. the >CO group test is positive
solution till a faint permanent brown
perform Tollen's test: ln a
precipitate is obtained and filtering of
clean test tube take 1 mL of
this precipitate or redissolving it in the Coloured dyes are AgNOg solution, add 2-3 drops of
minimum quantity of dil HCI). A red produced by diazo dil. NaOH solution. Add dil. NH3
colour is given by most phenols. coupling reaction by tillthe precipitate is almost
primary aromatic amines. completely dissolved, and add a
few drops of a solution of the given
(b) Phthalein reaction: Take a dry
substance. Warm gently with occasional
test tube, add about 0.1 g of the given
shaking. A silver
substance, a few crystals of phthalic
minor is seen if the aldehyde
anhydride and 2 drops of conc. HzSO+. functional group is present
Warm carefully for 1 minute. Then cool, and
add NaOH solution carefully in excess. give
(3) Test for Amide group: Boil
characteristic colours in alkaline medium; e.g.
phenolphthalein is pink, fluorescein formed 0.1g of the substance with 2 mL of
NaOH solution. Evolution of NHs
from resorcinol is fluorescent.,etc. confirms -CONH2 group. lf no
characterisiic test is obtainbd the
(c) Carbohydrate: To 1ml of aqueous compound isprobably an alcohol or
solution of substance, add 2 drops of hydrocarbon, or ester etc.
molisch's reagent and then carefully add 2 ml
of conc. H2SO4 along the sides of the test
tube. Allow to stand. A red violet ring at the
junction of two layers, confirm carbohydrate

Record the experiment, observation, and inference in a tabular form shown below.

Experiment obseruation lnference

Answer the following questions -

1. Why do the aromatic compounds give a sooty flame?
2. Amines are basic in nature but amides are not. Why?
3. Why are the aldehydes more easily oxidized than the ketones?
4. What are Tollen's and Fehling reagents?
5. Phenols are acidic but alcohols are neutral molecules, why?

TL
 compound by UV-Vis
ExpERTMENT No. G: characterization of an organic/inorganic
and lR sPectra.

Theory:
studies'
can be characterized by UV-Vis and rR spectroscopic
An organic or inorganic compound
radiation with matter'
are based on the interaction of the erectromagnetic
Both spectroscopies
because they contain erectrons
that can be
Morecures absorb radiation
uV_vis absorption: (400-750
levels by the absorption of energy at (i) visible wavelength
raised to higher energy (150-400 nm' i'e'
nm), producing absorption specrr*
in vislnle region; tiii uv wavelength
absorption spectrum in UV o- o* transition: Electrons in a
higher energy) producing "gion'
high .n.rgf (short wavelength) to
excite them
o-bond iequire radiation of
single covalent
producing o- o transition in uv ,."gion,""'r: "-
;' t*^titi"t at 122 nm in CH+' n- o* transition:
excited at a lower
in Cl, o and ru t'e ihe non-bonding electrons can be
Lone pairs of electrons - transition:
o. transition at"fZg nm in CH3CI'
"' 't*
energy than o-bonded electronr, ".g'-n- easily, e'g'rt - n. transit:"1"i:i:i
bonds can be excited relatively
Electrons in double or triple
nminCH2=611,.at1'80,2oo,255nminl,3.butadienebecausedelocalizedn-electronsrequlre
for excitation. cr,roroprror", rt is a fu.nctionar group having caharacteristic
ress energy
absorptioninvisibleorUVregion,e'g.c=t!,-No2,.N-N,nitrosoandcarbonylgroups,etc, pronounced effect qn
do not absorb signiiicantry in UV region but may have
Auxochrome: They CHa etc' d-d
of the molecules to which they are attached' e'g' oH' NHz'
the absorption absorb in the visible region
Many transition metal complexes with organic ligands or
transition:
of d erectrons fiom rower d revers to rrigtrer d revers in octahedral
due to the excitation transfer traniition: Here
fierd producing row intensity broad bands. charge
tetrahedrar
an orbitar in the and an unfilled orbital of the metal'
an erectron 'gand
is transferred between
absorption bands''gand
or vice-verso, producing more intense
follows the absorption of
absorption: Besides the change in electronic energy that
lnfrared
,rro-.irr"d with variation in the vibrational energy of the
radiation, there are also changes
in rotational energy'
atoms in the molecule and changes
molecule' At
from the different modes of vibration and rotation of a
rnfrared spectra originate
pm the radiation has sufficient energy to cause changes in the
wavelengths below 25 (4000-400 cm-l)'
levels of the molecule, producing ,irorption in lR region
vibrational energy producing rotational
in the rotational energy levels,
and these are accompanied by changes in rR spectrum by
region (200-io c;-r1. For a vibrationar mode to appear
spectra in far_infrared in dipole
of energy from the incident radiation, it is essentiar that a change
the absorption
momentsoccursduringvibration'Therefore'vibrationoftwosimilaratoms'e'g'oxygenor the lR region' whereas
(homonucrear aiatomic morecures) wi, not absorb in
nitrogen morecures
e'g' HCI' co have only one
vibrational mode called the
diatomic molecul es
of the bond along the bond axis' ln angles to
heteronuclear polyatomic
stretching mode---- periodic ,tr.tJing,
molecules, stretching and bendingo'
ilto''ation (displacements occurring at right
the bond axis) vibrational modes are observed. Two types of stretching vibrations are
syrnn'uetric and osymmetnc vibrations. Four types of bending vibrations are scissoring, rocking
and ouot' of, piome funding, wagging and twisting. ln general, the number of fundamental or
normrafl modes of vibration is given by 3N-5 for non-linear and 3N-5 for linear molecules, where
l'{ = numher of ato'rns. The characteristic lR absorption bands of some functional groups are as
fo{l,ons:

C4 ald,ehyde 1720-1i+O cm-l; C=O ketone L7O5-L725 cm-1; C=O ester L700-1750 cm-1; C=O
aald 1650 cm-1; C.N 21OO-225A cm-1; S-H 2570-2600 cm'L

Procedure: '

For UV-VIS: Prepare 1 x 10-1 M solution of the given compound in water and record UV-Vis
spectrum from 200-750 nm. ldentify Lr,, (maxima) and find out the corresponding moJar
absorption coefficients.

For lR: Record lR of the given compound using KBr in the range 4O0O-400 cm-1. ldentify
prominent bands such as carbonyl, azo, amino etc. Report the intensity of various bands, i.e.
report as s (strong), m (medium), w (weak) and sh (shoulder).

Answer the following questions:

1. Can you explain why the stretching frequency of C-O bond observes at much higher
wave number than that of Cr-O bond?
2. Which source is used in the UV-Visible spectrophotometer and in the lR spectrometer?

13
 6'5
of a polymer- Preparation of Nylon
EXPERIMENT
NO' 7: Synthesis

have.
Theory L ^.rrnn 6 These two nylons

rhe two most important

kinds:i.11':i.l:ilH: ,?: n: il!"*'-JliT';;;'ii"ou.''o
t:tn' y;';Jil
,'il ldenticat properties'
tn" u"ited States by Wallace
Car'*;';
carothers'
first. lt *"
'nutnl"Ol" oo'""-' ti I

o
trylon 6'6
hexane-1 '6-diamine adipoyl dichloride

the numb:,,:I, you how..:",-.^*:i;TTidijJ;

from A.B monomers,
For nylons made

tr]t'fi *i[:#*:ff *i"r'**;

ril."I;:$t[:"]*tii:lt"Uq+f
monome' r'"
atoms'
the :i:'T;T;n"o*"t'
carbon
For nylons made
in diamine monomer'
and
a how many carbons
B 'xri* *t"':tll:"";"il;.;
numbers ttrrv* monomer'
the diaci-Jor diacid chloride
are in

i1ffiyfl:ffi:H,lll,$'"-,J,:'T:i'Ti?::::T::'-*'l":"trff"h*;[1':-i;i::J"':$
to makenyron,'
',.r,"*
from an amlnc
",l"j,:';T.il:'il':|il'i[iT[;h**;i:"]$'ffi':1""ji:T:-1i
is making nYlon
PolYmerization'

Procedure 10 mL of
^ ,4 e_hoyanediamine). Pour
rer u *v
,;'iH: }ll'(J;l'lii'ii'l "*' o' s' u'ii' n c a the
r

il:: ffi :f lUa T5%::sorut,"" ;l';:1$:"fl'T

oi ,aip"vr crrtoride
(d1rr"',"0 in
.cyclohexane
solventl) to
the slightly tilted
beaker' Two
add 10 mL of ,, ,"*. ,n"
wa* of
u, oor-n* -,":il.
hexamethylenediaminu
}il,'::ilil f l;'il:
* :i'...":l [ :::,1.,HI ]il :{;:il*:'
io,*, an d th el:
aye rs raise
thecenter and srowlv
,,
interrace. Using
a copper-w''"
::::li.t;:'iil:'il-H;ur, can be drawn 'u'i
f'r
i,*::Ji:T1r1ff;r:: *d1*il::;[1]:i:.H;::ili., several times
with
Rinse.-tfe rope
pu*ing;;;.;
nr oroo.n bv remainder of
feet. The strand..n of wire, vigorously stir the
many
paper,o*, dry. with ,n. 0,"."
* and wash the
polymer
lay it on a the riquid
water and porv*lr. Decant Use a
to tor* .dditional the nylon in the sink'
the two_phase system *o'o'"t'd
o"l'"
water. Altow,nt o"',n"'"""
thoroughly with 14
waste container'
Answer the following questions

1. Why does nylon make such good fibers?

2. Draw the structure of the nylon obtained by replacing hexamethylenediamine with p-
phenylenediamine in the above synthesis.
3. Draw the structures of the monomers required to make nylon 6,10.
4. Draw the structure of the lactam monomer required to make nylon 7.

EXPERTMENT Nd.8: Spectrophotometric determination of l.",and concentration of

KMnOn/KzCr2O7.

Theory:

This experiment is based on Beer-Lambert's Law. But here the colour of KMnO+ or KzCrzOz
aqueous solution is due to the charge transfer transition. No additional reagent is required to
add to develop the colour whose absorbance or O.D. is to be determined. The tr.n,, of either
KMnOa or KzCrzOz aqueous solution can be. determined spectrophotometrically, and then
determine the absorbance of a series of 4-5 solutions of known concentration to make a
calibration plot (a plot between absorbance and concentration). By using the calibration plot,
the concentration of the unknown solution can be determined from its absorbance.

Requirements: Prepare Lx10-2 M solution of either KMnOq or KzCrzOz in distilled water. Dilute it
to prepare 5 x L0a M KMnO+ or L x L0-3 M KzCrzOt.

Procedure:

A. Determination of l*r, of KMnOy'KzCrzOi Take distilled water in one cuvette. Switch on

the instrument and wait 5 mins. Set the wavelength to 400 nm. Set the display to%oT,
and adjust the left knob till the display reads 0 with the cuvette-holder empty. Now
place the cuvette with water inside and close. Adjust the right hand knob till the display
reads l-00. Now either 5 x 10a M KMnO* or 1 x 10-3 M KzCrzOt may be inserted after
removing the water, and the %T may be read off. Using the display selector the
absorbance or O,D. may also be read directly. Then Set the wavelength to 410 nm,
repeat the above steps to measure the O.D. at 410 nm. Repeat same procedure by
selecting the wave length at the intervals of 10 nm up to 550 nm for KMnOa or 480 nm
for KzCrzAt Plot absorbance ys wave length and find out l.r,, i.e. the wave length at
which maximum absorbance is obtained.

B. Determination of concentration of KMnOe/KzCrzOt: Prepare 4-5 solutions of either

KMnO+ or K2Cr2O7 of different concentration using 5 x LO-a M KMnOa or l- x 10-3 M
KzCrzOt as given below:

15
 :l i: s ;:#1?'i
i';,:i i'-lH:.:lh**:H, T i.f"'""'-ffi#
the absorbi:t:r"ffi:il.t?,l" i.ne a unknown solution
of
[
distilled water
o*"r.,'.'"
n'f KM n oa n
*::m: fl: ::':r]:";"'";;;;.,
:J
?fr :;: : -T :""ff
[L',;:
ppm'

following questions:
lrrer the following
Answer
:*ii:*:i; of Mn/Cr in
fi concentration
i.. rs the molar extinction'::"'::::'::"T:Hril,i:"
be used
; i.n this Procedure
KMnO4/K2Cr2O7?

strength of ligands
of ligand filed
EXPERIMENT
No.9: Determination

rheorv: (about *0.:"-10:-T,i::':rJtll

visible light
, ^r..cnrhs tTilJex
-- absorbs corour in the
the magnitude
Transition metal
complexes depends on
.o*0,"*"1, ,iI."'o' * '1r"":ilt:"J#'""r"fr" ."..0'.-
tt;o;;; co*pt"* of weak
ligbnds

octahedral the colour "t

uo*t' the value stronser o'
Field splittinel. l'-il::J:*]-:;l;
;;' tr m"'on*
x
*i;*",.,'ton ; a

l'*::':1 ::::'ll ; :" of various

;u
i'
".x,: **,T :i I the strength
Yi: i u''nu '0"*'"oi"t"meter'
.o.pt"*"r-ot p.rti.rtr, order'
various
in the t""nding or descending
ligands can be""*O of
given complexes
procedure: of different
-_^^h^rnmeter.
prepare solutions si*it.'tv record the
spectrophot"T"t;:.j:"i#i;::ilr,,,n"
the )r max tii.::il"
complexes'
in the order or
First standardize
particurar ,,,""r",ni1i"r, to-'^*l'^*"'o'o il ;;;"wn)
)tmaxto'unttno*ngiven'o"tnuJlnecomplexes(Knownandunkno
ligands'
strength of the
questions: splitting (10D4)'
Answer the following .
.--^-^irr,rle of crvstal field
particular
l.Definecolourofthecomplexbasedonthemagnitudeofcrystalfie as strong ligands for a
weak as we*
series considering
2.write spectrochemical
metal comPlex'
 trihydrate.
EXPERTMENT NO.10: Synthesis of potassium tris-oxaratochromate(ilr)

Theory:
formula, t<r[cr(c,oo)3]'3H2o' lt is a
potassium t,s-oxaratochromate(ilr) trihydrate has chemical in its 3d
green complex having cr(lll) ceniral metal ion with three unpaired electrons
dark is a
;";*;i" with t32geo' configuration' oxalate ligand
orbitals. The complex has octahedral of potassium
active. lt is prepaied by the interaction
weak field ligand. The complex is opticJtly to cr(ilr)' The reaction
with chromium oxarate. oxaric acid is used to reduce cr(vr)
dichromate
involved is as follows:

2KE[Cr(CzOa):] + 14COz + THzO

KzCrzOt + THzCzO+ + ZKzCzOt)
and oxalic acid'
potassium dichromate, potassium oxarate monohydrate
chemicars Required:

Procedure:
12.5 mmol) and oxalic acid
oMakeasolutionofpotassiumoxalatemonohydrate(2'39'
(80-100 mL)'
dihydrate (5.5 g, 43'6 mmol) in water small Portions with
o To this solution add solid potassium
dichromate (L'9 g' 6'45 mmol) in
s
sorution nearry to dryness. on cooring deep sreen shinv crvstals of
. :""ltt#:H'[-; will be formed'
potassium tns-oxalatochromate (lll) trihydrate
Determine the % yietd'
o Filter the solid .;;;, by pressing it between filter paper'

Answer the following questions:

L. Draw the optical isomers of the complex'

2. ExPlain whY it is coloured?
of the complex'
3. Calculate spin-only magnetic moment

its merting
preparation of p-nitroacetaniride and determination of
EXPERTMENT NO. 11:
Point.

Theory:
of erectrophilic aromatic substitution'
Nitration of an aromatic compound is an
exampre
Nitroniumion{Noz*}attackstheringandnitrocompoundisobtained.
acid'
nitric acid, sulfuric acid' glacial acetic
chemical required: Acetanilide, conc.

t7
 ilX i:t i: :ffi l.i i''
li
fjiq :; il
:';'
-i,1 ;:'T iT:'.t* T i"'11
:'-
lli'i Y,- fu:
l,fl i ;o
oL,rt"n *','t *-'io""t'* 9""'-:'rlLTl'1i]r1,"Lltl"'i":X'T'1i:
dropwise [care,n"rio for 40 min and then t?JJ i"";:; remains
has been added'
'ilil"-;'xture ^t::*:;cetanilide
il',:r:i,x'$,.:11fl
I,tgiilil:fpoint'':lHti*:t'1"Jff,"TIIJJ[i;;::i;;;';'anddrv
Determine melting
on porous plate'

Reportcolourandm.p.ofthesampleandattachasampleinyourrecordbook
questions:
Answer the following
chiefly gives m-product' benzoic acid' chlorobenzene'
Nitration of aniline nitration of- nitrobenzene,
ot"rnono
Write the main O'"i'*

as osazone
NO' 12: Test of carbohYdrate
EXPERIMENT
through their osazone
tplon
can be easily tested
Theory: carbohydrate

rN--NH-\-/
d -:t:-\=--*---gl
*ffi*
H-foH
+ *r*'*n{)
v
--------'>
*_+_oH
rr-t-oH t-oH
l-- \o'^. . acetate' phenyl
hydrazine' acetic
-L^*"u"'Jlodium
Chemicalrequired:Glucoseoranyothercarbohydrate,SooturttclLgL9Lv,r.
acid.

Procedure:
'ilT:'ill
'l1::1,:,i:"',1;:';:lT',JJir"fiii+:Jf;
:"il:::!i::iJixll'[L-*'riff *':-"t Take 2-3 m[ of
anl';;;;-; in minimui.'-'''nount :l
1 g orroo,u* acetate
frask, transfer
jfft l], Hffi il rri; y***ul:r iij :;ffi ;;:'i;:
point'
il: tno note the melting
: :,ilr I:1T
;o'*,nr,"r. iu[r, t""tct the t"';;;i'v "ntl
crystals should
.00..;;
questions:
Answer the following rrr,.rose.
between glucose ^^r
and fructose'
to distinguish
1. Suggest a method
structure of mannose
l-8
2' Write
EXPERIMENT NO. 13: Determination of calcium in chalk/tooth paste using EDTA

Theory

Calcium may be determined by complexometric titration with ethylenediamine tetraacetic acid

(EDTA) which forms 1:1 complex with most metal ions. Usually disodium salt of EDTA is used.
The end points are obtained using indicators appropriate to the specific metals. For
determining calcium and magnesium, the indicator Eriochrome black-T (EBT) is useful. A small
amount of magnesium is essential for the indicator to function and is usually added to a buffer
solution. The reactions involved is:

ca2* + H2Y2- -+ Cay2- + 2H*

The indicator also forms complexes with Ca2*. The free indicator is blue in colour. The
Ca-EDTA complex is more stable than the Ca-indicator complex. As EDTA is added to the
buffered (pH = 10) solution of Ca salts in presence of Eriochrome black-T, the EDTA reacts with
free Ca2*ions. The end point is a sharp colour change from wine red to blue.

The results are reported in mgs of CaCO3 per litre (or in ppm).

Procedure:

Prepare a 0.L % W/V solution of calciu m carbonate as a standard. Weigh out about 0.1g of
CaCOg into the standard L00 mL volumetric flask, and dissolve it in a minimum quantity of
dil. HCl. Make up to the mark with distilled water.
Pipette out 10 mL of the solution into a clean conical flask and neutralize excess acid
present by adding about 2 mL of ammonia solution, and 5 mL of ammonia / ammonium
chloride buffer solution and 2-3 drops of indicator. Titrate it against the EDTA solution
supplied, tillthe colour changes from wine-red to blue.
Weigh -0.1 g of chalk and transfer it to 100 ml flask. Add few drops of HCI and make it upto
the mark. Take 10 mLof the solution and titrate as of standard solution.

Report the result in parts of CaCO3 per million (mg / litre).

Answer the follbwing questions -

I ,,\"rite different units of hardness?

: 3.e 1-rPACnameandstructureof theindicatorused.Whatkindof indicatoristhis?
3 ,', -, :-e C -sodium salt of EDTA is used and not its tetra-sodium salt?
: .', -:: ::'= .cle of buffer solution in this experiment?

19
EXPERIMENT NO' 14: DYe PreParation

TheorY

woad prant, was used to dye

Dyesarecompoundsusedtoimpartcolortoothersubstances.Dyeswereinusebefore burial
pigment extracted from the
recorded history. rndigo, a to dye blue jeans. Tyrian
lndigo is used today
over +ooo v",,, ago'
cloths for Egyptian mummies mollusks were needed
from Mediterranean mollusks' Rpproxi"t"rv 9000 the
purple was derived
ilr.rin, extracted from madder root was used to dye
ay.
to give one gram of dye. The red Revorution, ir',. ,"a caps
and trousers of French
in the American
red coats of British sordiers
soldiersintheFrenchRevolutionandviolinsofAntonioStradivari.

/;V+""')iyil':hn
.,=.q-i..\
UL5-D e\,.(J u".(-ilv''
bHo Tyrian purple
lndigo Alizarin
visibre right. when one looks
at the light
some waverengths of
corored compounds absorb white right m'lnus the waverengths
absorbed by
object, tr,e eve sels to thg
refrected from a corored appears as the color complementary
a colored chemical/object
the object. Therefore,
wavelength it absorbs'
Azo dyes are
an azo linkage (-N=N-) as part of its chromophore'
An azo dye is defined to
possess and
.rorn.,,J amine t' tniline is reacted with NaNO2
a primary "tr'
made in two steps. First, with a strongly activated
,.r,. su.ona,-,^. diazonium sart is reacted
HCr to give a diazonium dye'
phenoxide to produce the azo
aromatic system such as
o
NI
NHz
N.ci ,A \-
\)
A NaNo2 ,\
ll
\/
I -------> 6)-*=*{
\ /
\-J
) \-/
V Hcl (aq)
an azo dYe
aniline diazonium salt

Procedure
5'0 mL of distilled
and 0.40 g of sutfaniric acid into a 25 mL frask. Add
prace 0.15 g of Na2co3 ice-water bath using a 100
mL
dissolve' Prepare an
water. warm ,r'.l" tr.r'r, until the
solids into a test
sorution in,r," ice-water bath. prace 0.2 g of NaNOz
beaker. coor the surfaniric acid NaNoz solution the cooled
Shake the tube to dissorve the NaNoz. Add
tube, Add 1 mL of water. into a 50 mL beaker'
prace 3 g of crushed ice and 0.5 mL oi.on.' HCr
surfaniric acid sorution.
Slowlyaddthesulfanilicacidlsodiumnitritesolutionwithgentlestirring. 20
Add 20 mL of 10% NaoH to a 50 mL beaker. Dissorve 0.35 g of
2-naphthol in the IO% NaOH. tf
necessary, warm the beaker on a hot plate to dissolve the
2-naphthol. Once the solid has
dissolved, coolthe solution in the ice-water bath.

Dip three strips of cotton cloth in the 2-naphthol solution.

Allow excess solution to drip off the
cloth' Then dip each strip in the diazotized sulfanilic acid solution. Again,
allow excess solution
to drip off the cloth. Briefly rinse the strips with running water. Dry the colored
cloth strips by
gently flowing air.

To prepare the dolid dye, pour the diazotized sulfanilic acid solution
slowly into the 2-naphthol
solution with gentle stirring' Continue to stir the mixture for 5 min.
Then cool the solution in
the ice-water bath. Using a Pasteur pipet, slowly add 20-25 drops of conc.
HCI to the solution,
with stirring, to precipitate the red dye. Collect the solid by filtration
and dry it.

Answer the following questions -

L' Using color complementarity, explain how you can make the yellowed
cloth appear white
again?
2' Why you have to use conc. HCI in the final stage of the preparation to precipitate the dye?
3' write the complete equation for the dye preparation. Give the lUpAc name for the dye you
have prepared.
4. Draw the structures of Melachite Green and Congo Red.
5. How can you prepare Congo Red in a similar procedure?

2L
 ti
/*^
J' {'r)
-r'-l

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