MIDLANDS STATE UNIVERSITY

DEPARTMENT OF CHEMICAL TECHNOLOGY PRACTICAL REPORT FORMAT

FIRST PAGE

NAME:

REG NUMBER:

LEVEL:

PRAC TITLE:

PRACTICAL NUMBER:

PARTNER:

LECTURER:

DATE:

AIM/S: (1 Mark)

Must highlight the goal/s of the practical- the overall objective of carrying out the practical.

OBJECTIVES: (3 Marks)

Must be SMART;

S..........SPECIFIC

M.........MEASURABLE

A.........ACHIEVABLE

R..........REALISTIC

T..........TIME FRAMED

They must provide an orderly series of simple steps to achieve the experimental aims.

SECOND PAGE

Literature review/Practical theory (5 Marks)

 (a) Introduces the practical by giving the theoretical background;
(b) Should be concise but informative of the practical to be done;
(c) The basis of the practical should be clearly reflected under this section;
(d) DO NOT JUST COPY EVERYTHING WRITTEN IN THE PRAC SCHEDULE;
(e) Presents any equations used and explains how the results are used with the equations to obtain
any experimentally determined values;
(f) Presents reaction mechanisms in organic chemistry practicals;
(g) Safety handling and disposal of the chemicals must be clearly stated and
(h) errors associated with the practical must be highlighted together with corrective measures to be
taken.

ON A NEW PAGE

Apparatus (1 Mark)

 A comprehensive list of all the apparatus used in the practical must be presented e.g. glassware,
spatulas, pipette etc.
Reagents (1 Mark)

 A table of reagents should be presented having the following information:

Chemical name Chemical formula Manufacturer Mass/ concentration

Instrumentation (1 Mark)

A list of all instruments used in the practical must be presented in a table shown below:

Name Model Manufacturer Use in the practical

Procedure (5 Marks)

 Must be written in the third person past tense: non personal;

 Must be detailed reflecting the use of each of the apparatus, reagents and instruments listed
above;
 Specific masses, number of moles, volumes and concentrations must be included in this section;
 Must be brief, referring to the lab schedule for the details and not reproducing it;
 Describe any modifications or additional details not in the schedule and
 Should state the number of runs used and the conditions under which they were run.
NB. Replicate analysis is a must.

Results (5 Marks)

 Make use of tallies, tables and graphs as appropriate;

 Present results under this section and not tables showing the masses of reagents used in the
practical. Where lab data is plotted directly and not processed otherwise, reference may be given
 to the attached signed results rather than copying out the data;
 Any result deduced from graphs (e.g. graph points used for gradients or values) must be clearly
shown on the graph.
 Line of best fit must be drawn using the least squares analysis

Data treatment/ calculations (10 Marks)

 Averages must be reported with measurement uncertainties;

 Balanced chemical reactions are a must;
 Limiting reagents must be identified and stoichiometric calculations must be used to come up
with theoretical yields;
 An appropriate error analysis should be performed and
 Measurement errors should be estimated and the uncertainty in final results determined.
NB. Be reminded that 'results' without measurement uncertainty are no results.

NEW PAGE

Discussion (10 Marks)

 All the final results and their uncertainties should be presented making a critical comparison to
what is expected theoretically;
 The discussion of results must be meaningful and reasonable. This is achieved through intensive
consultation of relevant literature to the practical;
 Possible sources of error should be discussed and a realistic appraisal of systematic error in the
practical (and possibly ideas for reasonable improvements based on that).
 If results differ or deviate from what is expected, an in-depth explanation must be given based on
good chemistry;
 A comment on the success or failure of the practical should be presented by evaluating whether
objectives were achieved or not and
 The implications of the results must be highlighted.

Conclusion (3 Marks)

A summary of results and a concise presentation of answers to objectives and aims of the
practicals.

Answers to questions

Applicable to practical schedules with questions.

NEW PAGE

References (5 Marks)
  Must be at least five;
 Must be presented in alphabetical order;
 These include textbooks, journals, periodicals, magazines and electronic sources with
authors;

 Must be listed using the following format:

Text books

Author's surname, initial (year) Title(underlined), edition. Publisher, place of publication. Pages

eg Nharingo, T (1999) Heavy metal analysis, 6thEd. Mambo press, Gweru pp 12-25.

Electronic text books

As above together with the website and the date the website was accessed.

e.g. Nharingo, T (1999) Heavy metal analysis, 6thEd. Mambo press, Gweru pp 12-25. Retrieved

from http://www...................................... on 12/02/2010.

Journals

Author's surname, initial (year) Title of article(underlined),name of journal in full, volume (issue): pages.

e.g. Chitsa, V (2005) Biosorption of lead using Moringa Olefeira seed. Electronic Journal of

Biotechnology 8(5): 478-487

 MIDLANDS STATE UNIVERSITY

DEPARTMENT OF CHEMICAL TECHNOLOGY

SAFETY REGULATIONS

DEPARTMENTAL MOTO:THINK SAFETY FIRST AT ALL TIMES

 INDEMINITY FORM

This form is to be signed by ALL students before they can use the MSU Chemistry laboratories

I..............................................................................declare that I have read and understood the Chemistry

department safety booklet.I am going to comply with the safety requirements stated in the booklet and
I shall also follow any additional safety precautions that are stated in different practical booklets which I
will be provided by the Department of Chemical Technology during the course of my studies at Midlands
State University. I also undertake to inform the department of any illness that I suffer from that may be
triggered off by some chemical vapors.I also declare that I have informed my doctor about the nature of
the vapors that may be emitted during any practical prior to any given practical session and that the
medical practitioner has recommended that I can do ALL Chemical Technology practicals witout damage
to my health.

Signed

Student....................................................................Date..............................................................

Laboratory Technician.............................................Date..............................................................
The chemistry laboratory can be a place of joy ,discovery ,and learning.It can also be a place of
frustration –and danger.

Although every effort has deen made to eliminate the use in these experiments of explosive,very
toxic,or carcinogenic substances,there is an unavoidable hazard ivnvolved in the use of a variety of
chemicals and glass apparatus.In experiments where a potential danger exists,you will find a Safety
Precautions section at the beginning of the experimental procedure.Read this section very carefully
before you proceed with the experiment.

Your skin and the delicate membranes of your eyes,mouth,and lungs are largely made of protein.We
hope that you do not have to experience firsthand the adverse effect that even 6M solutions-not to
mention concentrated solutions-of acids and bases have on protein.The eyes are aspecially sensitive to
acids,bases,and oxidizing agents and must be protected at all times.In addition,the open flame of a
Bunsen burner presents a constant hazard to clothing and hair.

It’s likely that you will experience frustration if you come unprepared to the laboratory,neglect to record
important data,or frantically try to write up reports an hour before they are due.You can minimize the
these problems by reading the experiments carefully beforehand,noting the critical data that must be
recorded,and throughlly considering the data while you collect it in order to avoid careless blunders.

We strongly advise you to learn and observe at all times the following laboratory rules and regulations.
By doing so you will minimize the potential dangers and frustrations of laboratory work, and maximize
the joy.

1.You must read each experiment thoroughly before entering the lab.If you do not ,you will waste a
great deal of time(both your own and your instructor’s),you may expose yourself and others to
unnecessary hazards, and you will probably not obtain reliable, useful data.(You will also routinely fail all
pre-lab quizzes if your instructor chooses to use them.)

2.Discard solids into the waste crocks.Never throw matches,litmus ,or any insoluble solids into the
sink.Wash down liquids into the drain with much water;acids and salts of copper,silver,and mercury are
corrosive to lead plumbling.

3.Leave reagent bottles at the side shelves.Bring test tubes or breakers to the shelf to obtain chemicals.

4.Read the label twice before taking anything from a bottle.

5.Avoid using excessive amounts of reagent-1 to 3ml is usually ample for test tube reactions.

6.Never return unused chemicals to the stock bottle.You may make a mistake from which other
experiments will suffer.

7.Do not insert your own pipets or medicine droppers into the reagent bottles.Avoid contamination of
the stock solutoion by pouring the solution from the bottle.
8.Do not heat heavy glassware such as volumetric flasks, graduated cylinders, or bottles; they break
easily and heating distorts the glass so that the calibrations are no longer valid.(see Figurre 1-4).Test
tubes may break if they are heated above the liquid level and liquid is then splashed over the hot
glass.Evaporating dishes and crucibles may be heated red hot.Avoid heating any apparatus too
suddenly;apply the flame intermittently at first.

SAFETY RULES

These rules are designed to ensure that all work done in the laboratory will be safe for you and your
fellow students.In addition to the rules listed here,your instution may have a set of rules that you will be
asked to read and sign as evidence that you have read them.

Your laboratory instructor should also point out the location and demonstrate the use of various pieces
of safety equipment for handling splills.

Finally, you should know where first-aid supplies are kept and where a telephone is located for
emergencies that require paramedical,fire,or police assistance. The telephone numbers of these on-or
off-campus services should be posted in a prominent place.

1.The most important rule is that safety glasses with side panels or goggles must be worn at all times in
the laboratory.Ordinary prescription glasses sometimes cover only parts of eyes and lack side panels
that protect the wearer from chemical splashes that might get into the eyes from the side.For this
reason, they should be covered by safety goggles.Contact lenses should not be worn in the
laboratory,even under safety goggles.By themselves they offer no protection from splashes and they are
considered unsafe even under safety goggles because various fumes-for instance,hydrogen chloride gas-
may accumulate under the lens and cause serious injuries .If you do not wear glasses, obtain a pair of
glasses or goggles from the chemical technology stockroom.In some procedures-such as heating a
crucible to dryness or evaporating an acid solution-be sure to wear safety goggles or to carry out the
experiment in a hood,which is provided in most laboratories for this purpose.

If any chemical comes in conduct with the eye,the most effective first aid is the immediate flushing of the
eye with copious amounts of tap water.You are seldom more than a few seconds from a faucet.Continue
flushing for at least five minutes and then consult a physician at once.If your laboratory is equipped with
eye fountains,familiarize yourself with their use and their location.

2.Fire is a constant present danger.Learn where the nearest fire extinguisher is and how to use it.Your
laboratory should also be equipped with a fire blanket and safety shower or fountain.

If your hair or clothing cath fire,smother the fire with a blanket or douse yourself in the shower.

3.Minor burns,cuts,and scratches are fairly manageable,show injuries to your instructor who will
determine what first aid is appropriate.If further treatment is required ;be certain that someone else
accompanies the injured person.
4.Bare feet are not allowed in the chemistry laboratory.Broken glass and spilled chemicals, such as
concentrated acids,are all too common on the floors of chemistry labs.In addition,we recommend that
bare legs,midriffs,and arms be covers with old clothing or preferably,with a laboratory apron or coat.

5.The vapors of a number of solutions are quite potent and can irritate or damage the mucous
membranes of the nasal passages and the throat.Use the technique displayed in figure 1-1 when you
need to sniff an odor.

6.In many experiments,it is necessary to heat solutions in test tubes.Never apply heat to the bottom of
the tube;always apply it to the point at which the solution is highest in the tube,working downward if
necessary.Be extremely careful about the direction in which you point a tube;a suddenly formed bubble
of vapor may suddenly eject the contents violently(an occurrence called bumping).Indeed, a test tube
can become a miniature cannon(see Figure 1-2.)

7.Avoid tasting anything in the laboratory as an eating place and do not eat or drink from laboratory
glassware.

8.Perform no unauthorized experiments.

9.Never work in the laboratory alone.

10.Beware of hot glass tubing- it looks cool long before it can be handled safely.

11.For reactions involving poisonous gases,use the hood,which provides suction to remove such gases or
vapors.

12.Neutralise spilled acid or base as follows:

(a)acid on clothing ,use diluted sodium bicarbonate solution; (b) baseon clothing,use dilute acetic acid;
(c) acid or base on the desk,use solid sodium bicarbonate for either,followed by water.

13.To insert glass tubing(including thermometers, long-stemmed funnels,thistles tubes,etc.) through a

rubber stopper,first lubricate the tube) and stopper with water or glycerol.Hold the tubing with a cloth
near the end to be inserted,and insert.
 CHEMISTRY SAFETY

A few hints on safety and techniques:

Acid:

Regard all concentrated acids as potentially dangerous.When diluting add ACID slowly to
water,NOT water to acid.

Do not carry bottles of concentrated acids by neck.Support the bottle with a hand underneath.

Do not pour concentrated acid down the sink.If acid is spilt,dilute with water,neutralize with solid
sodium bicarbonate,and wipe up immediately.

FIRST AID:external :dilute with plenty of water,sponge with weak borax or sodium bicarbonate solution.

Internal: do not induce vomiting, drink large volume of water and seek medical attention
immediately.

ALKALI: see ammonia and sodium hydroxide.

FIRST AID:external:dilute with water,sponge with 4% boric acid solution or 5%ammonium chloride
solution.

Internal:do not induce vomiting,drink large volume of water, weak acetic acid or lemon
juice,seek medical attention immediately.

Eyes:wash with large volume of water,follow with 4%boric acid bath.

AMMONIA:Concentrated ammonia solution is often under consideradle pressure,particularly in

warm,weathetr.Open the bottle cautiously,awy from face,near an open window or in fume
cupboard.Ammonia fumes,although not corrosive,can cause respiratory distress and should be treated
with caution.

FIRST AID:plenty of fresh air.If splashed on sensitive skin or in eyes,treat as alkali burn.
AMMONIUM NITRATE:Often used in the preparation of nitrous oxide,this substance may explode if
strongly heated.In preparation of nitrous oxide,it is safer to use a mixture of ammonium sulphate and
sodium nitrate.

BROMINE:Best bought in 1ml ampoules.A safe way of opening these, is to place in the bottom of tall
measuring cylinder and tap with an iron retort stand rod until broken.Disposal of excess
bromine,removal of fumes in jars etc,shake with sodium bicarbonate solution.

FIRST AID:vapour:smell meths.,alcohol,or dilute ammonia solution.Wash mouth out with 1% sodium
bicarbonate solution.

Skin:wash firstly with water,secondly with sodium bicarbonate solution,and thirdly with alcohol.Treat as
normal burn,but if excessive seek medical attention.

Eyes:vapour;wash with 1%sodium bicarbonate solution,seek medical attention.

BUNSEN BURNERS:Do not panic if tube comes off and flame appears at the end of the tap,it cannot burn
back to the cylinder! Just turn off the tap.

Ware blue flame in sun-lit lab,practically invisible.

Ware long hair,especially if lacquered near Bunsen flame.

CARBON BISULPHIDE:Very inflammable,volatile,and toxic.Will ignite on hot surface.Sometimes

encountered in the preparation of rhombic sulphur crystals.

CHLORINE:The preparation from concentrated hydrochloric acid dripped on potassium permanganate

crystals easiest to contlo.(N.B. use pure potassium permanganate, and make sure acid is
hrydrochloric,not sulpuric!)

FIRST AID:Treat as for bromine.

CYLINDERS GAS:(oxygen and hydrogen)

Do not over-tighten valve,and get expert help if valve is stuck.Never lubricate valve or any part of
oxygen cylinder.Always turn on cylinder and adjust gas flow before conctrating to apparatus.

DISPOSAL OF WASTE:Have metal bin for disposal of solid aste.Do not put powerful oxidizing agents(qv)
into waste bins.For disposal of phosphorus,potassium,sodium,mercury,bromine,see under appropriate
headings.

DISTILLATION:e.g fractional distillation of crude oil.Remember distillate is inflammable and use deep(6”
or 15cm) test tube to collect.Never attempt to distill ether or mercury.(q.v)

ETHER:heavy and extreamely inflammable vapour.Been known to ignite from a lighted Bunsen or spark
20ft away.can also be ignited by an electric hot-plate.Store in a dark bottle,in a cool cupboard.
FIRE AND FIRE EXTINGUISHERS:Make sure you know the position and use of the laboratory fire
extinguisher.In case of fire DON’T PANIC.Orderly exit of pupils if the fire is minor,smother with sand or
asbestos blanket.Pupil on fire:cover with blazer,roll on ground.

GAS CYLINDERS:see under Cylinders,gas.

GUNPOWDER: All gunpowder recipes are very dangerous.

HALOGENS: see under Bromine,Chlorine,Iodine.

HYDROGEN:Never use a Kipp’s apparatus as a source of hydrogen for burning in air or reduction
experiments.Preferebly,use a cylinder,but if not available use smallest volume apparatus,test issuing
hydrogen for purity by collecting small test tube full and lighting at safe distance.( weak ‘pop’ and quite
burning,probably O.K).Use a safety screen for hydrogen experiments.

HYDROGEN PEROXIDE:Strong oxidizing agent,(q.v),fire hazard if concentration greater than 50 vols in

contact with combustible material.

HYDROGEN SULPHIDE:Dangerous gas,as poisonous as hydrogen cyanide in the same

concentration.Paralyses senses of smell,so is not detected after a while.Prolonged exposure to small
concentrations can cause pulmonary and gastric illness.

IODINE: Do not mix with ammonia solution,since a dangerous percussive explosive is formed when
dry.Vapour toxic, treat as for bromine.

MANGANESE DIOXIDE:Must be pure if used in the production of oxygen from potassium chlorate.Test
small quantity before use by class if in doubt.

MECURY:Treat with respect! Volatile,can be absorbed through the skin,is an accumulative poison.Work
over a tray.If spilt pick up with a mecury supoon,(copper foil mercury amalgam) and sprinkle flowers of
sulphur over residue.Never distill.

MECURIC OXIDE:When heated to show oxgen,use a long test tube, small quantity, and concentrated
flame, to encourage mecury to condense in upper parts of test tube and not escape into the lab.

NITRIC ACID:Extrmely corrosive when concentrated.For FIRST AID, see ACID.

NITROGEN DIOXIDE:Very toxic gas,prepared by action of concentratied nitric acid on copper.Sometimes

used as ‘brown gas’ in diffusion experiments.

FIRST AID:treat as for bromine vapour.

NITROUS OXIDE: see ammonium nitrate.

OXIDISING AGENT:Potassium permanganate,hydrogen peroxide,sodium peroxide, potassium chlorate-

examples of strong oxidizing agents.Can cause fire or explosion if mixed with oil,glycerine,cotton
wool,paper or other combustible material.Never mix with carbon, sulphur,phosphorous,concentrated
sulphuric acid,or powdered metals such as magnesium or aluminium.

OXYGEN:Ware heating corks or rubber bungs in apparatus containing oxygen, as they may burn
vigorously.Easiest preparation is from action of heat on potassium permanganate.

PHOSPHORUS:White or yellow,stored under water,burns spontantaneously in air.soluboe in grease, so

beware of greasey gas-jar lis in experiments involving it.Fumes formed on burning toxic.Excaess
phosphorus can be disposed of in copper sulphate solution.

FIRST AID: burns,treat with 1% copper sulphate solution bandage and seek medical attention.

POTASSIUM:Stored under xylol(inflammable),or liquid paraffin(much the safest).Work on a dry bench

with dry tongs,and knife,well awy from water when cutting it.Use a rice grain size piece for action on
water etc,and work under a large beaker or glass trough.

Small shavings of potassium can be disposed of in new meths.Do not use standard lab. Stock as it might
contain water from density experiments.

Do not touch any bottle of potassium or sodium which appear to have ‘dried out’. Inform Head of
Department immediately.

POTASSIUM CHLORATE: see under oxidizing agents.

POTASSIUM PERMANGANATE: see under oxidizing agents.

SAFETY SCREEN:Should be used in all hazardous experiments, or where there is any doubts about the
safety of an experiment.Can be manufactured from old rear windscreen.(obtainable from car-breakers.)

Minimum pupil distance should be about a metre .sweep a metre rule around the bench,anyone who
received a clout is too close!

SODIUM: as for potassium.(q.v)

SODIUM HYDROXIDE:Strong alkali(q.v). Much heat evolved when dissolved in water.Extremely

dangerous for eyes.

SODIUM PEROXIDE:Reacts vigorously with water.Extreme fire hazard,see under oxidizing agents.

SULPHURIC ACID:Very corrosive when concentrated.Large amount of heat released when

diluted.Particularly important to follow dilution instructions under ACID.
Safety –Code of Conduct in the organic Chemistry Laboratory.

1.0 Responsibilities:Request information if in doubt.Bring to the attention of your supervisor any

conditions which you think could lead to accident or injury.Safety in your place of work is your
responsibility.

2.0 Personal conduct

(a) Fire:-Know the location of the nearest fire alarms,extinguishers,blankets and showers.In the
event of a fire alarm being given,turn off all gass suppliers and electrical equipment,close
windows and doors,and walk out of the nearest safe exit.Dry sand and not carbon dioxide
should be used on alkali metal or hydride fires.Carbon dioxide should be used on other chemical
fires.

(b) Warnings:Inform others in the vicinity when carrying out operations of abnormal risk.Do not
perform such operations un observed.

3.0 Laboratory dress and conduct:Wear suitable safety spectacles( obtainable from the Chemical
Technology Department stores) or visors when manipulating vessels,under external pressure,flame
heated glassware, boiling liquids or at any other time when there is potential eye risk.If you do not
wear prescription glasses,wear safety spectacles at all times when in the Chemical laboratories in
which such work is carried out by yourself or others.Wear shoes(not sandals)and laboratory acid
proof coats (obtainable from Chemical Technology Stores) in chemical laboratories when work is
carried out by yourself or others.Do not drink or smoke in teaching laboratories.Wash hands after
handling corrosive, carcinogenic or radioactive substances, and before leaving the laboratory.Know
the location of the nearest First Aid Box and Eye irrigation bottle.A tidy laboratory reflects the
competence of the work performed in it.Keep gangways,exists and safety equipment free from
obstruction,and keep benches tidy.Do not leave items of clothing in places where they present a fire
or accident hazard,and do not keep briefcases,bags,books etc on shelves from which they could
topple onto apparatus.
 Mop spillages immediately.Wash apparatus and put it away as soon as it is no longer
required.Replace reagents in their proper places and use them only in the near vicinity of the
shelves to which they belong.Use clean,dry dropping pipettes for trnsfering small amounts of
liquid,spatulas fo slolids.Do not contaminate reagents or permanent
apparatus(balances,ovens,etc).Replace stoppers and seals on the reagent bottles at once-many
reagents decompose rapidily if left open.When using communal facilities,label your own material
identifiably.Do not carry out experimental work alone without the knowledge and specific
permission of the meber of staff for whom that work is being done.

4.0 Use of Facilities

(a) Apparatus:

Do not use cracked,chipped,insulator-frayed or otherwise obviously faulty apparatus when

sound replacements are available.Do not use make-shift appliances.Obtain the right equipment
,set it up carefully and correctly,and avoid undue mechanical strain,particularly on
glassware.Wrap glassware in a cloth before pushing, pulling or twisting manually.Grease Quickfit
joints when working with strong alkali.

(b) Gas

Only transport cylinders in trolleys.Clamp them so that they cannot topple.Do not operate a
cylinder without the key being in the main valve throughout if the cylinder is of the key-
operated type.Close the main valve when the cylinder is not in use.

(c) Burners:

Extinguish burners on leaving the laboratory,no matter how temporarily.If it is necessary to

leave a burner on without using it to heat anything,turn off the air so the flame is clearly
visible.Do not light a burner without ensuring that volatile flammable substances are not being
used in the vicinity.

(d) Water/condensers

Wire on ruber tubing if carrying water to and from apparatus if it is to be left overnight.Turn off
taps not in use.If left overnight,fit apparatus requiring water for cooling with a fail-safe cutout.

(e) Disposal of Residue:

Thoroughly flush drains with water after they have been used in the disposal of large quantities
of water-miscible residues.Use large bottles and not drains for the disposal of large volumes of
water immiscible residues.

(f) Flammable Materials:

 Most common organic solvents are flammable and those with a low boiling point(e.g ether)
present a particular fire hazard.They also offer an explosion hazard when confined in small
spaces above their flash point(which is normally lower than their boiling point).For example, 6ml
of benzene can produce an explosive atmosphere in a chamber of 1m3,and that explosion could
be triggered by a spark of static electricity.Do not heat these solvents over an open flame except
when arrangement has been made to confine the vapour within a condenser.Even then,it is
better to use electrical heating mantles or waterbaths.Extinguishing all naked flames in the
vicinity of open work flammable solvents boiling below 70oC.Do not place reactive
chemicals,particularly strong oxidizing agents and finely-divided metals like palladium on
charcoal in waste bins where enough heat can be generated to cause combustion.Filter paper
socked in permanganates,peroxides,etc.come into this category.Volatile
solvents(ethers,spirits)must not be stored in fridges unless such fridges are labelled’spark proof’.

(g) Toxic or corrosive liquids and Solids

All chemicals unless the contrary is known, should be regarded as potentially toxic and
corrosive,and handled accordingly. Use pipette bulbs in pipetting strong acids,bases or any
other liquid.NEVER USE YOUR MOUTH.Aromatic
liquids(benzene,toluene,xylene,aniline,nitrobenzene,etc)and chlorinated
hydrocarbons(methylene,chloroform,carbon tetrachloride,etc) are cumulatively and therefore
insidiously toxic. Their vapors are hamful, and in addition the aromatic liquids are harmful by
absorption through the skin.Excercise appropriate care when handling these solvents:do not use
them in unventilated rooms and avoid skin contamination by aromatic solvents.

(h) Toxic or Corrosive vapours :

Carry our all work involving toxic or corrosive gases and poisonous substances with a significant
vapour pressure at room temperature , or reagents which can interact to form toxic gases,in
ventilated fume hoods.Do not remove chemical reagents found beneath fume hoods into the
open laboratory.

(i) Carcinogens:

Many chemicals are carcinogenic, i.e. cause cancer.They may do this by inhalation, absorption or
ingestion. It is not possible to give a list of the numerous individual chemical carcinogens,but the
following classes of compound present a cancer hazard: any hydrocarbon of 4-6 fused aromatic
rings,(e.g. haphthacene,pyrene,chrysene,benzetracene,benzphenanthrene); any azo
dye(recognizable by ‘azo’ in the name,e.g N-methly-N-nitrosovinylamine); any nitro derivative or
amine of systems containing 2 or more aromatic rings
(naphthalene,biphenyl,stilbene,anthracene,phenathrene,fluorine).Keep containers of such
substances closed except when withdrawing contents.Carry out any operation involving risk of
inhalation in ventilated fume hoods.Avoid skin contamination.If occurring,treat by copious
irrigation with cold running water.
(j) Labelling:

Label wash bottles and all containers of chemical reagents with the name of the contents.

(k) Vacuum or High-pressure Apparatus:

Tape or cage apparatus under external or internal pressure if to be left for lengthy periods(e.g
Dewer vessels, desiccators).Do not evacuate flat-bottomed flasks or bottles(with the exception
of especially thickened glass apparatus such as Buchner Flasks).They are not designed to
withstand a vacuum and may implode.

(l) Safety screens:

Perform potentially violent reactions and distillation sunder vacuum, behind Perspex safety
screens.

AVOID SHORTCUTS-GOOD LUCK!

 MIDLANDS STATE UNIVERSITY

DEPARTMENT OF CHEMICAL TECHNOLOGY

HCT 204: CHEMICAL INSTRUMENTATION 1

EXPERIMENT 1:

Determination of the distribution of trace heavy metals in urban roadway dust in Gweru.
INTRODUCTION

Dust is useful as an indicator for pollution. Various parameters can be measured in dust samples chief
among which are the heavy metals like Pb, As, Cu, Zn, Ni, Fe, Mn, Al to name a few.When introduced
into the human body by inhalation, ingestion or through diffusion via the skin(in the form of salts like
ZnCrO4 ) these metals cause various maladies ranging from skin lesions through gastro tract problems to
severe brain damage.

People working in dusty environments are exposed to high levels of various toxic metals. The dust that
enters the body through inhalation is mostly that which is airborne. In protected areas like open
verandas and shades at garages, flea markets and bridges , this air borne dust gradually settles down at
a rate dependent on their densities. For dust particles of similar composition, the density should vary
directly with particle size. Small particles are air –borne for longer periods than larger ones and end up
being inhaled into the human body.

The ease with which dust samples can be taken enhances its use as a pollution index. It is found almost
everywhere and can be sampled using very simple equipment.

Dusts along roadways are due to a number of sources. Because of the presence of metals in the earth’s
crust, the existence of these metals in roadway dust is to be expected. Automobiles contribute direct
exhaust emission and tyre wear particles which probably come from body rusting and ablation from the
interior of the exhaust system. It is apparent that streets with high traffic densities should also have high
metal levels.

The construction and demolition of structures or buildings that has been painted with heavy metal –
based paints contributes a wide range of metal s into the vicinity of roadways. Some industrial activities
like welding, spray painting, metal casting emit toxic metals into the environment.

LITERATURE REVIEW

A literature review is a general survey of the work that has been carried out elsewhere and published in
journals by other workers on levels of trace heavy metals in roadway dust.

You are supposed to carry out a literature review and report your findings in less than two pages.
Remember it is very important to take note of references in your literature review.

REAGENTS AND CHEM ICALS REQUIRED

Analytical grade (AR) reagents are to be used throughout.

Nitric Acid SG 1.40

Perchloric Acid 72% (w/w)

Hydrochloric Acid SG 1.34

Standard solutions for various metals (1000ppm, spectrosol)

PROCEDURES

Sampling

Identify a sampling site of your choice and prepare an appropriate sampling plan.

Carry out your sampling according to your sampling plan by scooping the dust with clean spatulas into
well labeled polythene bags and tie with strings.

Samples should be collected at 2m intervals starting from the edge of the road going away from the
road.The total number of samples to be collected should be enough to allow one to draw a good graph
of the metal distribution.

Standard Solution Preparation

Using 1000ppm commercial stock solutions transfer 10ml into a 100ml volumetric flask and dilute to the
mark with distilled water. This gives a 100ppm working standard for each metal.

Prepare from the working standard appropriate calibration standards by serial dilution measuring 1ppm;
2ppm; 4ppm; 6ppm; and 8ppm. Prepare composite standards. As and Hg standards should be prepared
according to the requirements of the methods used to analyse these metals i.e. hydride vapour
generation and mercury vapour generation.

Sample Treatment

 Air-dry the dust samples at room temperature, i.e 24-30oC.

 Weigh the dry sample on an analytical balance and sieve the samples through a series of
stainless steel of diameter 600,400,200,100 and 50 microns.

 Weigh each fraction and put it in a well labeled bag.

 To 0.4000g portions of the prepared dust in 250ml beakers add distilled water to form a sherry.

 Add HNO3 (5ml) and HCLO4 (0.5ML)

 Heats the mixture on a hot plate until a residue remains. Add 2M HCL (2.5) to the residue and
transfer quantitatively the contents to a 100ml volumetric flask bringing to the mark using
distilled water.

 Analyse the samples by Flame AA or Graphite furnace AA depending on the level of each
element in the samples. Use the following instrumental condition in your analysis by FAA.
METAL WAVELENGTH(nm) BAND PASS(nm) LAMP FLAME TYPE
CURRENT(mA)

Cd 228.8 0.5 4 Oxidising

Cr 357.9 0.2 5 Reducing

Cu 324.7 0.5 4 Oxidising

Fe 248.3 0.2 5 Oxidising

Mn 279.5 0.2 5 Oxidising

Ni 232.0 0.2 4 Oxidising

Pb 217.0 1.0 5 Oxidising

Zn 213.9 1.0 5 Oxidising

Express each fraction as a percentage of the bulk sample and the metal levels as mg metal/kg dry
sample.

Draw graphs showing the relationship between;

i. Weight of fraction and particle size

ii. Metal levels and particle size

iii. Metal level and distance from the road

Discuss and conclude your results.

References

References are expected to come from your literature review.

EXPERIMENT 2:

Ultraviolet spectrophotometric determination of Aspirin, Phenacetin and caffeine and Anadin tablets
using solvent extraction.

PRINCIPLE

Caffenol and Anadin tablets are a mixture of aspirin, phenacetin and caffeine. Each of these substances
has characteristic absorption in the ultraviolet region, with the principle maximum lying at 227 for
aspirin, 275nm for caffeine and 250nm for phenacetin.In the procedure, a powdered tablet is dissolved
in methylene chloride and the aspirin is separated from the phenacetin and caffeine by extracting it into
aqueous sodium bicarbonate solution. The separated aspirin is back –extracted into methylene chloride
by acidifying the aqueous layer and is then measured spectophotometically at 277nm. The phenacetin
and caffeine that remain in the original methylene chloride layer are determined in a mixture as
described in analytical texts in Chapters on UV/VIS spectrometry according to Beer’s law. According to
Beer’s law, when two absorbing species in solution have overlapping peaks, the total absorbance. A is
the sum of two absorbances. For two absorbing species,

A=axbcx + aybcy

OR A= Exbcx + Eybcy

Where A is the total absorbance observed ax and ay are the absorptivities of X and Y, Ex and Ey are the
molar absorptivities of X and Y in grams per litre of the solution and b is the path length. For two
unknowns, two measurements have to be made and absorbencies at each peak will be,

A1=Ax1 +Ay1 =Ex1bcx + Ey1bcy

And Ax2 + Ay2 = Ex2bcx + Ey2bcy

Concentration of x and y can be obtained by solving these equations.

Equations

A HCO-3 A CH2CI2 A (277nm)

P CH2CH2 P (250nm) + C (275nm)

Reagents and Chemicals

Provided CH2CI2, 4% (wt /vol) NaHCO3 solution (chilled), concentrated. HCl, 1M H2SO4.

To prepare

Standard solutions. Prepare individual standard solutions of about 100mg/L, 20mg/L and 10mg/L each of
aspirin, phenacetin and caffeine in methylene chloride as follows:

Weigh about 25mg (to the nearest 0.1mg) of each, transfer to 250ml volumetric flasks, and dissolve to
volume with methylene chloride. Dilute 10 and 5ml of this solution to 50ml in 50ml volumetric flasks to
prepare the 20 and 10mg/h solutions, respectively.

PROCEDURE

Weigh accurately and record the weight of one tablet. This should be equivalent to about 220mg aspirin,
160mg phenacetin, and 30mg caffeine. To minimize required dilutions and save on solvents, cut the
tablet into quarters and weigh out one –quarter portion to be analysed. Crush to a fine powder in a
beaker. Add, with stirring, 20ml methylenechloride; then transfer the mixture quantitatively to a 60ml
separatory funnel, rinsing all particles in with a little more methylene chloride. Extract the Aspirin from
the methylene chloride solution with two 10ml portions of chilled 4% sodium bicarbonate to which has
been added two drops hydrochloric acid, and then with one 5ml portion water. Wash the combined
aqueous extracts with three 10ml portions of methylene chloride (to remove traces of water) into a
50ml volumetric flask and dilute to the mark with methylene chloride. Then dilute further a 1ml aliquot
of this solution to 50ml with methylene chloride in a volumetric.

Acidify the bicarbonate solution (aqueous extract), still in the separatory funnel, with 6ml
of1MH2SO4.This step should be performed without delay, to avoid hydrolysis of aspirin. The acid must
be added slowly in small portions. Mix well only after the most of carbon dioxide evolution has ceased.
The pH at this point should be 1 to 2 (pH test paper). Extract the acidified solution with eight separate
10ml portions of methylene chloride and filter through an ethylene chloride wet paper into a 100ml
volumetric flask. Dilute to volume. Then, Dilute further a 5ml portion of this solution to 25ml with
methylene chloride in a volumetric flask.

Record absorbance versus wavelength curves for the standard solutions and unknown solutions
between 200 and 300nm. (This step may be deleted if you do not have a recording ultraviolet
spectrophotometer). Does the wavelength of 277nm appear to be the most suitable wavelength for the
determination of aspirin? Do the wavelengths of 250 and 275nm appear to be the best wavelengths for
the measurement of the absorbance for the mixture of phenacetin and caffeine? Explain. Using the
absorbencies of the standard and the unknown aspirin solution at 277nm) calculate the percent aspirin
in the caffeine and /or Anadin tablets and the number of milligrams of aspirin per tablet keeping in mind
the dilutions.

To calculate the concentrations of phenacetin and caffeine, the absorbencies of phenacetin and caffeine
standards and of the methylene chloride extract of the sample must all be read at both 250 and 275nm.
/using these absorbencies, calculate the percentage phenacetin and caffeine in the APC tablets and the
milligrams of each per tablet. See Chapter 13 for the spectrophotometric determination of mixtures.
(G.D Christian, Analytical Chemistry)

Note: Aspirin tends to decompose in solution, and analysis should be performed as soon possible after
preparing solutions.
EXPERIMENT 3:

Qualitative Gas Chromatographic analysis of a multicomponent mixture of pesticides.

Introduction and Overview

Gas Liquid chromatography (GLC) is a type of chromatography in which the mobile phase is a gas, such
as nitrogen, helium, etc, and the stationary phase in an inert liquid. The sample is usually in liquid form,
but is flash vapourised as it is injected into the instrument and is maintained in the gaseous state
through the instrument. The major components of a gas chromatograph are shown in block diagram
below:

Carrier Column Detector

Flow Injection
Oven (heated)
Controller Part
Gas
(heated)

Electrometer

Recorder
Carrier Gas or Mobile Phase

The carrier gas chosen depends; on the detector to be employed; nitrogen or argon is used with the
most popular detector, the flame ionization detector (FID). The carrier gas is supplied at a reduced
pressure from a large gas cylinder equipped with a pressure regulator. Often the carrier gas is filtered
through tubes containing a drying agent, a molecular sieve and oxygen scrubber to remove moisture,
impurities and oxygen from the prior to its entering the column. The flow of controller is needle valve or
other device used to control the gas flow rate. In some instruments a rotometer is used to measure the
the actual flow rate. A flow rate of 75cm3 per min, is most often used for 6,4mm o.d. columns, while a
flow rate of 25cm2 per min is used for 3,2 o.d. Columns.

The injection Part

The sample is introduced into the GC through the injection Part, a small hearted chamber capped with a
septum. The sample is introduced by means of a small calibrated syringe. The septum is pierced by the
Syringe needle and reseals when the syringe needle is withdrawn /typical volumes injected into packed
columns are 1-3ul.

The injection part temperature part temperature should be high enough (e.g. 2200C) to vapourise the
sample instantly (i.e. flash vapourisation). Sample vapourisaton should be rapid so that the vaporized
sample is swept by the carrier gas into the column as a discrete’’plug’’

The column

The column where the actual chromatographic separation occurs is enclosed in an oven that maintains
the desired temperature.

A conventional ‘’packed’’ column is filled with a granular solid support coated with a thin layer of liquid
stationary phase. Separation occurs by differences in the distribution of the various sample components
between the carrier gas and the liquid stationary phase. (s/p).

The s/p is normal coated evenly on the surface of the solid support with a solution of the liquid phase
and then evaporating off the solvent. The solid support must have a uniform pore diameter and a large
surface area. These properties are needed to support an adequate coating of stationary liquid phase and
provide good contact with the mobile phase. The particles should be of regular shape with good
mechanical strength to permit an efficient, well-packed column. The solid support can be made from
silica and other materials. Columns can be metal or glass. Glass is preferred because it is inert towards
most organic compounds. After packing a column is conditioned before its use by passing carrier gas
through it at elevated temperatures to remove volatile impurities.

The Detector

The function of the detector is to sense when a compound is leaving the column and to provide a signal
that is proportional to the concentration of the compound of the compound in the carrier gas stream.
Several types of detectors are available. The FID is the most common and responds to all organic
compounds. The detector is heated to the temperature needed to keep the sample compounds from
condensing.

The Electrometer

The output from the detector is a very small electric current. This is fed into an electrometer which
amplifies and converts the detector output to a voltage that is large enough to be recorded.

The Recorder

The recorder records the voltage from the electrometer as a function of time to give a chromatogram
showing the separated sample components as peaks in the chromatogram.

Theory of Gas liquid chromatography

Chromatographic Efficiency

The width of chromatographic peaks is a measure of the efficiency of chromatographic system. The
system includes the entire instruments and not just the column. The ability to obtain sharp, narrow
peaks is often expressed in terms of a plate number. A large value for a plate number indicates high
chromatographic efficiency and excellent separation ability.

The plate number, N, is related to the length of the chromatographic column, L, by the equation,

H = L/N

Where H is the plate height.

Effect of flow rate on chromatographic efficiency:

The Van Deemter equation is the classical statement of the effect of flow rate on chromatographic
efficiency. The simplified form of this equation is

H = A + B/u + Cu

Where u is the average linear gas flow rate in cm/sec, and A, B and C are constants. A plot of H versus u
shows that H has a minimum value at a certain value of u. This is the optimum value of u for
chromatographic separation.

----------------
 u opt

Temperature and temperature programming

Temperature is a major factor in adjusting conditions for a satisfactory separation. When sample
components elute rapidly and are incompletely resolved, lowering the column temperature will slow the
elution and probably improve the peak resolution. If a mixture containing both high and low a
component is to be separated, the temperature needed to separate the boiling compounds may slow
the separation of the high –boiling components too much. Late eluting peaks will be broader and
resolution often poor. In such cases temperature programming can be used. In this technique, the
column temperature is increased linearly with time at a preset rate. The more volatile sample
components are separated at the lower temperatures while the higher- boiling compounds gradually
move at a faster rate through the column so that their peaks appear earlier on the chromatogram.

Principle of method

An acetone extract of the specimen is partitioned between hexane and saturated brine. The hexane,
containing the non polar pesticides (organophosphorus, organochlorine and carbaryl), plus fat, is
cleaned up on a wood’s column and then examined by the GLC,TLC Brine solution containing the polar
pesticides is extracted by ethyl acetate and extract examined by GLC,TLC, e.t.c. If only one type (polar or
non-polar) is being sought the full procedure need not be followed, the appropriate parts are selected.

Procedure

Put 10g of soil sample and 10g anhydrous sodium sulphate and 50ml acetone in a250ml beaker and
homogenize by stirring. Filter the contents through a fluted filter paper and place on water bath with fan
to evaporate to approximately 5- 10ml.

Transfer the residue to a 250ml separating funnel containing 100ml of saturated sodium chloride
solution and rinse the beaker with 2 x 5 ml hexane and 1 x 5 ml acetone adding the rinsing to the
separating funnel. Shake vigorously for 2 minutes, allow the layers to separate and run the aqueous
layer into the original beaker. Transfer the hexane to a 250ml separatory funnel.

Re-extract the aqueous layer twice or more, each with 10ml hexane. Wash the combined hexane with 2
x 10 ml brine solution by gentle shaking, and add the washings to the main brine solution, which is then
reserved for the extraction of the polar pesticides.

If necessary, dry the combined hexane with a little solid anhydrous sodium sulphate and then decant
onto 1.5g celite in a 50ml beaker, washing the sodium sulphate with a little hexane. Evaporate the
hexane at low temperature, with occasional stirring until a homogenous hexane-free friable powder is
obtained and transfer to a small wood’s column for clean up, Fill in the large wood’s columns with
Florasil and saturate with hexane. Elute from the small columns into the large columns using dimethyl
sulphaxide (DMSO) (6ml).Elute from the large columns with 50ml hexane containing 15% of ether.
Concentrate the eluate to 10ml and reserve for GLC analysis.

Extract the combined brine solution with 3 x 50 ml ethyl acetate (vigorous shaking for 5 minutes) drying
each extract successively with the small quantity of anhydrous sodium sulphate and evaporating
successively in a 150ml beaker, finally to almost dryness. Dissolve in acetone and make up to 10ml, and
reserve for GLC.This solution contains the polar organophosphorus pesticides.

GLC ANALYSIS

It is advisable to inject first on FID, then NPD and possibly after appropriate dilution, on ECD.

Confirmation of identity can sometimes be partly accomplished by injection on more than one column,
but if possible, TLC confirmation should be done.

FID – Flame Ionisaton Detector, non selective, detects both polar and non polar pesticides.

NPD- Nitrogen Phosphorus Detector; selective, detects polar pesticides.

ECD- Electron capture Detector; selective, detects non polar pesticides

Stationary Phase: 10% OV101 and 2% OV 17

GLC CONDITIONS

Inject Pot temperature: 2300C

Column temperature: 2400C

Detector temperature: 2500C

INJECTION PROCEDURE

Inject 1ul of standard pesticide, parathion until there is a consistent retention tin. Inject 1ul of blank
prepared the same way as the sample extracts. Inject your unknown sample and record the retention
time. Calculate the relative retention time. Inject the various available standards and identify the
unknowns by calculating the relative retention time.

Questions

1. Why is anhydrous sodium sulphate used in the extraction procedure.

2. Comment on the use of the two solvents; acetone and hexane.

 3. Why is it important to make sure that no samples in acetone are injected while using ECD as
detector?

Discuss and conclude your results.

EXPERIMENT 4:

Quantitative Gas Chromatographic Analysis of alcohol in a multicomponent mixture (Internal standard

technique)

Principle

The basis for quantitative analysis by Gas Chromatography is that the area under each peak is
proportional to the concentration of the sample compound, assuming constant conditions of column
temperature, flow rate, etc

The areas of peaks are easily measured using modern electronic integrators. Manual methods include
triangulation and cutting and weighing. These manual methods are naturally less accurate.

Most instrumental errors can be eliminated by using the internal standard method. In this method, a
constant amount of a pure compound (the internal standard) is added to a specific volume of the
unknown sample and to several synthetic mixtures containing different amounts of the compound to be
measured.

The synthetic mixtures are chromatographed first and a plot is made of percent compound versus ratio
of peak area of the compound to the peak area of the standard. The unknown is then chromatographed,
the peak areas of the compound and internal standard are measured, and their ratio is calculated. The
percentage (or concentration) of the compound in the unknown sample is then read from the graph.
Results from this technique can be satisfactory reproduced even if operating conditions (such as flow
rate and temperature) have varied slightly from run to run.

Apparatus and Reagents

 1. A gas chromatograph with a Flame ionization detector will be used for this experiment. Please
become familiar with the operating instructions for the particular instrument available,
including, the direction of the power supply control unit and the record recorder paper available
for the recorder. (A good chromatographic column for the experiment uses Porapak Q
stationary phase. The column is operated at approximately 1800C giving retention times around
5 minutes).

PROCEDURE

Preparation of calibration curve solutions

1. Internal standard (n- propanol) – Dilute 0.4ml n-propanol in distilled water and reconstitute to
one litre volumetric flask. This solution is 0.04% n-propanol in water.

2. Prepare a 5 %( m/v) ethanol solution in distilled water. The specific gravity of this solution
should be 0.9759 at 15.60C at 200C

3. Intermediary Standards

Prepare as follows:

1ml of stock (solution) standard to 100ml water= 50mg/dL

a) 2ml of stock standard to 100ml water gives 100mg/dL

b) 3ml of stock standard to 100ml water gives 150mg/ dL

c) 4ml of stock standard to 100ml water gives 200mg/dL

d) 5ml of stock (solution) standard to 100ml water= 250mg/dL

e) 6ml of stock standard to 100ml water gives 300mg/dL

f) 7ml of stock standard to 100ml water gives 350mg/ dL

g) 8ml of stock standard to 100ml water gives 400mg/dL

4. WORKING STANDARDS

Dilute each intermediary standard (5.0ml in a volumetric flask using the 0.04% n- propanol.Store
in a refrigerator.

SAMPLE PREPARATION

a) Heparin anti-coagulated blood is preferred, although any other anti-coagulant can be

used.

b) Using a pipette add 5ml of sample (blood) into a 50ml-volumetric flask.

 c) Into the same volumetric flasks dilute the sample to the mark using the aqueous
internal standard

7. GLC Setting

a) Connect the column according to instruction in the manual and optimize for about 30 to 60
minutes.

b) For Pye Unicam 304, the following would be a general guide line and can be used as a guide line
for other instrument type.

Column temperature : 1800C

Detector temperature : 2500C

Injector temperature : 2300C

Hydrogen pressure : 18psi

Air pressure : 5psi

Nitrogen pressure : 26psi

Chart recorder speed : 300mm/hr

Chart range : 10mµ

8. Analysis of Standards and Samples

a) Inject the highest standard and adjust the instrument for the best resolution.

b) Inject each standard and each sample and record peak areas of both ethanol and n-propanol

c) Calculate the ratios of ethanol peak areas versus those of n-propanol.

d) Calculate the concentration of alcohol in your samples in mg/dL

NB: A standard curve can be used to calculate the concentration in each sample, or one can use
the standard that has the nearest ratio to that of sample.

Questions

What are the advantages of using the internal standard technique?

Why did you choose your method for area determination?

Could you have predicted the exit order of the components without determining their retention
times? What factors determined this.
 Do your chromatogram exibit ‘tailing’ what causes it and what conditions could be changed to
prevent it?

Reference:

1. Fritz and Schenk ‘Quantitative Analytical Chemistry’ 5th Edn., 1987.

EXPERIMENT 5

UV-VIS Spectroscopy: Colorimetric Determination of Phosphorus in Cola Drinks

Phosphorus is a form of phosphate can be determined calometrically by formation of a complex with a

molybdate compound in acid solution. The reaction proceeds as follows:

7H3PO4 + 12(NH4)6Mo7O24.4H2O 7(NH4)3[ PO4(MoO3)12] + 51NH4+ 51OH- = 33H20

The colourless hexavalent molybdenum phosphate complex is reduced to a blue pentavalent form by
ascorbic acid in acidic medium and can be measured spectrophotometically at 830nm.

REAGENTS

Make a stock solution (1 litre) of 1000ppm phosphate using potassium dihydrogen phosphate in
deionised water. From the stock solution, prepare a working standard solution (100ml) of 10ppm
phosphate.

Dissolve 1.00g of ammonium heptamolybdate (NH4)6Mo7O24.4H2O in 50ml deionised water.

Dissolve 1.75g of ascorbic acid in 100ml of deionised water.

Dilute 17ml of concentrated sulphuric acid in 200ml of deionised water.

Prepare a reducing solution by mixing 39ml of the ammonium molybdate solution, 60ml of ascorbic acid
solution, and 125ml of the diluted sulphuric acid solution in a 250ml volumetric flask and filling to the
mark with deionised.

Sample

A cola soft drink is provided. The sample has been let to stand at atmospheric pressure for at least 24h
prior to the practical (why is it important?). Prepare a diluted sample solution (20 x dilution) in a
volumetric50ml volumetric flask. Fill to the mark the deionised water.

Procedure
Pipette in 50ml volumetric flasks suitable quantities of the working standard solution in order to obtain
calibration solutions with final concentrations of 0, 0.8, 1.6, 2.4, 3.2, 4.0 and 6.0 ppm PO43-

Pipette 1ml portions of the diluted sample solution into the three 50ml volumetric flasks. To each of the
nine flasks; add 20ml of the reducing solution. Fill up to the mark the deionised water. Heat the
calibration and test solutions for 45mins in a water bath at 500C. In the meantime, ensure yourself that
the colour of the cola sample will not interfere in the spectrophotometric quantification of the blue
pentavalent molybdenum phosphate compound at 830nm. How is this done? Is there any interference
from the food colouring?

Measure the absorbance of each solution at 830nm.Plot a calibration curve with the absorbance as a
function of the phosphate ion concentration. Calculate the phosphorus (P) content in your sample.
Evaluate the precision of the analysis (assuming no error in the calibration procedure), by reporting the
95% confidence limits for the result. Assuming an average consumption of 35bottles (at 300ml) of cola
drink per person and year, how much phosphorus is needed annually to meet the production demand in
the cola industry in Zimbabwe?

ACKNOWLEDGEMENTS

D.Lozano-Calero, P.Martin-Palomeque, S.Madueno-Loriguillo, J.CHEM.Educ.1996, 73, 1173-1174

Water Analysis for Heavy Metals

Making of Calibration Standards

You are provided with stock solutions of 1000ppm Cu, Zn and Pb.Make three calibaration standards for
Cu, Zn and Pb. The calibration Linear range for Cu is 2ppm-8ppm, Zn is 1ppm-5ppm and Pb is 5ppm-
25ppm.

Preparation of Water Sample

Take 50ml of water sample and put in a 250ml volumetric flask. Put 5ml of aqua regia to free bound
metals. Top up to the mark with distilled water.Analyse the sample using FAAS.

NB: Do at least three replicate analysis of your sample

Inorganic Practicals

New spectrochemical series experiment.pdf Nitro and nitrito cobalt complexes.pdf

Synthesis of Cr(11) acetate hydrate.pdf Cabonato and chlorato.pdf

Co(111) uv-vis spectrochemical series.pdf Cr experiment Spectrochemical series.pdf

CT202 Practical.pdf inorganic Cu(1) compound.pdf

CH213 PRACTICAL

Preparation of pinacole hexahydrate and pinacolone

Give mechanisms for the formation of (3) and (4) . the first is a reduction by a radical coupling
using a dissolving metal in aprotic solvent and the second is an acid catalysed wagner-
meerwein rearrangement.

(a) pinacol hexahydrate (3)

dry magnesium (5.0g) and anhydrous benzene (5ml) are placed in a dry 250ml two-necked flask
fitted with a 50ml dropping funnel and a double surface condenser protected by calcium chloride
tube.make a solution of mercuric chloride (5.6g) in dry acetone(25ml)and place it in the dropping
funnel. Run in all of it. If the reaction can not commence after a few minutes as frequently
happens, heat gently on an isomantles. If the reaction still does not start, grind the magnesium
with a sharp glass rod until it does. This is signaled by the solution turning cloudy and refluxing
vigorously.remove the flask from the isomantles until the reaction stops refluxing (may take
about 30 minutes). Reflux on the isomantles(10 minutes). Add a mixture of dry benzene(13ml)
and dry acetone (12.5g) /16ml, warm on an isomantles for 1hour.the magnesium pinacolate
swells. Remove the calcium chloride tube. Introduce water (13ml) through the condenser and
shake. Heat on the isomantles or water bath for further 3o minutes with occasional shaking

allow the mixture to cool to 323K and filter at the pump (celite). Return the solid to the flask and
reflux with a fresh portion of ordinary reagent benzene(30ml) for 10 minutes. Filter as above,
combining filtrates.

Evaporate the filtrate to half by evaporation at the rotorvapour. Add water (15ml) to the residue
and cool in ice with stirring. After 30 minutes filter the product at the pump. Wash with ordinary
benzene(10ml). Dry in a desiccator. Determine the yield and m.p.

Do not use the whole sample in the next step.submit what you do not use for marking.

(b) Pinacolone

cautiously add conc sulphuric acid (15ml) to water (50ml) in a 150ml distillation flask with
stirring and then add pinacole hexahydrate (10g). distill slowly over a gauze into a flask
connected to the condenser by a matching adapter. continue until no more oily drops of
pinacolone come over. Wash out the distillation flask and repeat with the remainder of your
pinacol hydrate, scaling reagent quantities appropriately.

Extract the combined distillates with diethyl ether ( 2x 15ml ) ( BEWARE of naked flames ) dry
over magnesium sulphate, filter and distil off the ether on a rotavapour. Using a micro-
distillation apparatus distil the pinacole with a micro-burner. Collect the fraction boiling ca 105o
in a weighed ampoule (obtainable from the stores). Note the pressure and boiling point.

Using a hot flame on the glassblowing torch, seal the ampoule at the neck. Ask a demonstrator to
show you how (if in any doubt). Turn off the air and turn down the gas in that order, leaving the
torch alight.

Weigh the ampoule and detach THE fragment. Calculate the yield of pinacole. Submit the sealed
ampoule for marking.
Record and comment on the IR and 1n NMR spectra of pinacolone.

Reading: Reduction by dissolving metals, e.g. texts by

i. House, H. Modern Synthetic Reactions 1972

 ii. Norman, R.O.C, Principles of Organic Synthesis, 1978.
iii. Cirruthers, Some modern Methods of organic synthesis, 1977

iv. Chemistry in Britain , 10 (3) 95-97 (

Problems

1. what would be the main final product and why if this series of reactions were carried out on
Acetophenone?
2. what is the role of HgCL2.

3. Pinacol when heated with hydrogen bromide gives a hydrocarbon which reacts with maleic
anhydride to afford C10H12O3. Explain

4.what would occur if the first reaction were carried out in a protic solvent ?. describe one other
reaction depending on radical anion coupling under aprotic conditions and one other reaction
depending on radical anion protonation.

EXPB1

Preparation of caprolactam(2-ketohexamethyleneimine)

This is a beckmman rearrangement which invovesthe conversion of ketoximes into N-substituted

acid amides by treatment with certain acidic reagents. In much the same manner CH3COCLor
PhSO2CL may be employed to effect the reaction. Examination of the product has shown that it
is always the substituent trans to the hydroxyl group that migrates, hence the beckmann
rearrangement may be used to distinguish between the syn (cis) and anti(trans) forms of
ketoximes. Furthermore the migration is intramolecular ie if the migrating group is asymmetric
there is no inversion of configuration in the rearrangement product.

(i) Cyclohexane oxime (2)

dissolve hydroxylamine hydrochloride(6g) and sodium acetate (8g) in water (20ml) in a 100ml
conical flask. Warm the solution to cool to 313K and add cyclohexanone(6g). close the flask
with a cork and shake vigorously for a few minutes. Observe and record your observations. Cool
the flask in ice and filter the crystals at the pump using a Buchner funnel,washing the resultant
solid with a little cold water. Recrystallise from pet-ether (323-333K). then dry the crystals in an
oven (below353K). record the yield,mpand IR of the product. Submit at least 50mg for marking.

(ii) caprolactam (2-ketohexamethyleneimine ) (3)

place cyclohexanone oxime (5g) in a 500ml conical flask and add 85%sulphuric (5vols conc
sulphuric to 1 vol water ) warm the flask on a hot plate (fume hood) and gently swirl the contents
until bubbles appear. Then remove the flask from the hot plate and allow the violent reaction to
subside.cool yhe mixture to 273K and then slowly add,with stiring 24% aq,KOH until the
solution is faintly alkaline to litmus.keep the temp below 283K during the addition. Remove the
ppt by filtration washing the residue with a little CHCL3.

Extract the aq alkaline solution with CHCL3 (3X50ml) and wash the combined CHCL3 extract
with water why? Remove the CHCL3 at the rotor vapor and purify the product by distillation
under reduced pressure. Consult your tutor for this.

Record yield , bp ,as well as mp and ir of the product.

Problems

1. cite major difference between the IR spectra of compounds (2) and (3)
2. what is the purpose of NaOAc in the prepation of (2)

3. briefly outline how you could prepare perlon (an important industrial polyamide fibre) from
caprolactam.

4. give two possible products from the beckmann rearrangement of Acetophenone oxime
EXP A4

Isolation of piperine from blackpepper

Piperine (1) is an alkaloid with a tertiary amide structure . it occurs in unripe fruit of black
pepper and kernel of the ripe fruit of white pepper and varies from 6-9%. In the following
procedure, the piperine is extracted with EtOH using a soxhlet extractor and converted into its
1,3,5-trinitrobenzene complex

Procedure

(a) piperine
extract finely ground black pepper (30g) with EtOH (210ml) in a soxhlet exractor for three
hours.filter the solution and remove most of the solvent on a rotary film evaporator. Add 10%
alcoholic KOH (30ml) and after 15 minutes filter off any insoluble material. Piperine should
crystallize out after standing overnight. Record the yield, mp and IR spectrum of your product.

(b) 1,3,5-trinitrobenzene complex

Piperine forms a solid complex with 1,3,5-trinitrobenzene in the ratio of 1:1. Use some of your
product to prepare this complex using the method given in Vogel (4thedtn p1094).and record the
melting point of your product. Submit samples of both products for inspection.

Problems

1. Explain briefly what purpose is served by the use of 10%KOH in this expt

2.show how the following degradative results A-H are consistent with the proposed structure for
piperine.
Expc1

Preparation of Benzilic acid (3)

HNO3 HO-
PhCOCH(OH)Ph → PhCOCOPh → (Ph)2C(OH)CO2
(1) (2) (3)

This is the base catalysed conversion of aromatic 1,2-diketones into salts of alpha
hydroxycarboxylic acids. The best known example is the conversion of benzyl(2) into Benzilic
acid ie:the Benzilic acid rearrangement. Kinetic studies show that the migration of the phenyl
group with its bonding pair of electrons, to the weakly positive carbon atom of the adjacent
carbonyl group is the rate determining step.

Procedure
(a)oxidation of benzoin(1) to benzil(3)
place benzoin (3.8g) and conc HNO3 (12ml) in a 50ml round bottomed flask. Heat the mixture in
a fume cupboard on a steam bath with occasional shaking for ca11/2hrs or until the evolution of
brown fumes stops. Pour into a stirred mixture of crushed ice and water, filter off the crystalline
ppt with suction and wash with water, why?. Recrystllise the solid from boiling EtOH (CA.7ml).
Record yield, mp,IR and UV of your product.keep what you do not use in the next step for
marking.

(b) rearrangement of benzil(2) to Benzilic acid (3)

place a solution of KOH (2.5g) in water (5ml) in a 50ml round bottomed flask and add EtOH
(7.5ml) with swirling. Then add benzil(2) (2.5g)-note the colour of the solution . boil under
reflux on a water bath for 15 minutes. Pour the contents into a conical flask and cool in ice with
swirling. Filter off the benzilate at the pump and wash it with a little ice-cold EtOH. Disssolve
the salt in water (ca25ml) add conc HCL ca 2drops with stirring and filter off the ppt.gradually
acidify the filtrate with conc HCL ca 4ml, until the liquid is acid to congo red paper. Filter off
the ppt of the title cmpd(3), wash it thoroughly with water(why) and recrystalise from boiling
water in the presence of activated charcoal. Record yield,mp,Irand HNMR. Submit samples (2)
and (3) for marking

Further reading

1. Norman, principles of organic chemistry 1978

2. Carey and Sundberg advanced organic chemistry

PROBLEMS

1. Benzaldehyde cannot form an enolateion.what then are the products when it isn treated with
base and how mechanistically, do they rise?

2. diketones which have alpha hydrogens undergo condensation reactions on treatment with HO-.
With clear mechanistic explanations, give the products of HO2CCH2COCOCH2CO2H under
hydroxide ions.

3.from a mechanistic point of view, outline the main similarity btwn the Benzilic acid and
pinacole rearrangements.

4. explain how,3-methyl-4-nitrobenzoic acid is formed from the tropolone

Expc4

Preparation of beta-dimethylaminopropiophenone hydrochloride

PhCOCH3 + HCHO + (CH3CH2)2 → PhCOCH2CH2N(CH2CH3)2HCL

(1) (2) (3) (4)

This is a base catalysed condensation of formaldehyde with ammonia or a primary or a

secondary amine and a compound containing at least one reactive hydrogen atom often an
aldehydes ketone or ester. The reactive hydrogen is replaced by an aminomethyl or substituted
aminomethyl group.

Procedure

Place dry diethylamine hydrochloride(3) (3.5g) powdered paraformaldehyde(2) (1g) and

Acetophenone(1)(2.95ml) in 100ml round bottomed flask fitted with a reflux condenser. Add

EtOH (4ml) containing two drops of conc HCL and boil the mixture under reflux for 11/2hrs.It

should then be clear and homogeneous but if necessary filter the solution through a preheated

Buchner funnel. Remove as much solvent as possible and then transfer the concentrate to a 50ml

conical flask and add ice-cold acetone(20ml) to the warm solution.allow the mixture to cool to
room temp and further cool in ice. Filter off the crystals at the pump , wash them with acetone

(2ml) and dry with suction. Then dry at 373K for half an hour. Recrystalise by dissolving the

product in hot absolute EtOH (4ml) followed by the slow addition of acetone (23ml) to yield

pure beta dimethylaminopropiophenone hydrochloride. Record the yield, mp and IR of the

product. Submit the product for marking.

 MIDLANDS STATE UNIVERSITY

DEPARTMENT OF CHEMICAL TECHNOLOGY

PHYSICAL CHEMISTRY (CT201) PRACTICALS

EXPERIMENT 1: CRITICAL MICELLE CONCENTRATION

INTRODUCTION
Ionic surface active materials, such as sodium dodecylsulphate (SDS) consist of two species of ion, an ionic head
group attached to a hydrocarbon tail (dodecyl-sulphate ion) and a counter ion (sodium ion).The way in which the
physical properties of a solution of a typical colloidal electrolyte, such as SDS, vary with increasing concentration,
alters when a particular concentration is reached. This concentration is known as the critical micelle concentration,
or c.m.c .The accepted explanation of this is that in the region of the c.m.c., aggregation of the long chain
electrolyte ions into quite large, charged units begins to occur. These charged units are typically made out up of
about 100 surface active ions forming a spherical unit, with the charges situated at the periphery and the
hydrocarbon tails in the centre .The adsorption of a considerable number of counter ions reduces the overall
charge and also the coulombic repulsion between the head groups.

APPARATUS

Stock solution (2x10-2 moldm-3) of sodium Dodecylsulphate glassware:

Either (a) surface tension (torsion balance)

Or (b) conductance bridge,

METHOD
-3 -3
Prepare a series of solutions from the stock solution provided over the concentration range 10 moldm to
-2 -3
2x10 moldm .To measure the c.m.c either measure the surface tension (γ) or the conductance (G) .If conductance
is to be measured also measure the conductance of the water used to prepare the dilutions. Subtract the
conductance of the water from the conductance of each of the test solutions.

RESULTS

(i) Plot a graph of γ against c

C.m.c ℓ

(b) Conductivity= K= Cell Constant x C

A= molar conductivity = K/C

= cell constant x G/C

Hence in (b) it is sufficient to plot G/C against √ c

 G/C

c.m.c √c

Estimate the c.m.c using your results and give a future for the likely experimental error.

EXPERIMENT 2: THE SOLUBILITY OF A SOLID SOLUTE IN AN IDEAL SOLUTION.

Aim
To construct the solubility curve of a near ideal system.

Theory

For a solid solute saturated solution, the equilibrium constant K, is just the mole fraction of solute in the saturated
solution. Hence the variation of with temperature is given by the van Hoff`s equation;

o
In x2 = -∆H + constant

(N2) RT
o
Where x2 is the solute mole fraction. Now ∆H can be split up into the sum of the enthalpy changes for two
processes:

Solid solute liquid solute saturated solution

o o
∆H for the first step is ∆H for the second step should be zero if the system is ideal, because in the mixing of two
ideal liquids there should be no energy changes.
o
Therefore, In x2 = -∆H fusion/RT + constant

When x2 = 1, i.e. pure solute, T is the melting point of pure solute, T o

o
Therefore, In x2 = -∆Hf (1/T – 1/To) (1)

In this experiment the system; naphthalene in toluene is to be investigated and the data compared with the
theoretical results assuming ideal behavior.

Procedure

Weigh between 14, 9 and 15,1g of naphthalene flakes into a boiling tube and add 6,00ml of toluene from a
o o
burette. Immerse the boiling tube in a beaker of hot water (70 C; note that the boiling point of toluene is 110 C)
and stir with a wire loop stirrer until the solid has dissolved. Place a thermometer in the tube, remove the tube
from the bath and allow it to cool in air, stirring fairly vigorously to prevent super cooling. Note the temperature at
which crystals first appear in the solution. Add a further 2,00ml of toluene to the test tube and repeat the above
sequence. Continue the process until eight crystallization temperatures have been recorded.

CAUTION- owing to the toxic nature of toluene, this experiment should be performed in the fume hood, and care
taken that no vapour is inhaled or any liquid spilt on the skin.
Calculations

1. Calculate x2 for each solution taking the density of toluene at room temperatures as 0,864g/ml.

2. Plot In x2 versus 1/T (K).

3. Draw on the same graph the straight line of theoretical slope -∆Hf/R

For naphthalene, ∆Hf = 19,079J/mol. This line will pass through the point corresponding to the melting of pure
o
naphthalene (x2 = 1) which is 80,2 C.

4. (a) Obtain ∆Hf and Tf for naphthalene from your experimental curve and

(b) Comment on the extent to which the naphthalene/toluene system approached ideal behavior and, using
your knowledge of the molecular structure of these compounds, where the results could have been expected.

Questions

How would such data be used in the construction of a phase diagram for a two component system?

*∆Hf = ∆Hfusion ; Tf = Melting point of naphthalene.

EXPERIMENT 3: THE THERMODYNAMICS OF ELECTROCHEMICAL CELLS

Objective

To measure the e.m.f of an electrochemical cell at a variety of temperatures and hence determine the
thermodynamic functions ∆G®, ∆S®, and ∆H® for the cell.

Introduction

It is readily shown from thermodynamics that

 E® = -∆G®/nF and (δE®/δT)p = ∆S®/nF

Consequently electrochemical potentials and their temperature variation provide an invaluable experimental
method of determining ∆G® and ∆S®, and hence K and ∆H®.

The cell used here is a Gerke Cell :

-
Ag(s) | AgCl(s) | Cl (aq) | Hg2Cl2(s) | Hg (l)

which has two distinct advantages: there is no liquid junction between the electrodes , and the e.m.f. does not
depend on any potentially varying activity ,but is always equal to E®. The cell reaction is :

2Ag(s) + Hg2Cl2 2Hg(l) + 2AgCl(s)

Note that the sign of the e.m.f for the cell as written is the polarity of the mercury electrode.

Method

Set up an ice-water bath into which the cell is placed , so that the bath liquid is above the liquid inside the cell
.Leave to cool to about 0°C , adding more ice as needed: it may take one hour or longer before the cell is at the
bath temperature . Stir the cooling bath from time to time .

Once the experiment has equilibrated , take three readings of the cell potential at one minute intervals, noting the
polarity of the cell and temperature .As the sign displayed by the voltmeter belongs to the electrode connected to
the Red/High/V terminal (sometimes confusingly labelled +), this enables the polarity to be determined .Mix some
of the ice-cold water with tap water to achieve a temperature a little above 10°C and re-immerse the cell in the
bath . Leave for about 20minutes , stirring from time to time. Carry out the determination of temperature , cell
potential and polarity as before .Repeat the procedure at temperatures of about 20° ,30° ,40° and 50°C , mixing
colder and hotter water to achieve the required temperatures , and allowing about 20 minutes for equilibration at
each temperature (add more hot water if necessary).

Note: only connect the voltmeter when taking the readings: disconnect when equilibrating.

Results and discussion

1. Deduce the electrode reactions and hence the cell reaction and it`s Nernst equation, proving that invariably E =
E®.
o
2. Plot a graph of e.m.f with temperature and determine the slope and value of E at 25 C. Calculate ∆G® and ∆S®
o
and hence ∆H® at 25 C. Compare these with values calculated from thermodynamic tables.
o
3. Deduce the direction of spontaneous change at 25 C.
EXPERIMENT 4: MEASUREMENT OF THE SURFACE TENSION OF A LIQUID BY THE BUBBLE
PRESSURE METHOD.

Theory:

When a bubble is formed slowly at the end of a capillary tube, radius r, which dips into a liquid to a depth d, the
pressure in the tube increases to a maximum which corresponds with a hemispherical bubble and then decreases
as the bubbles break away.

The maximum bubble pressure is given by

P = dℓg + 2γ/r (1)

Where ρ is the density of the liquid to be measured, g is the acceleration due to gravity, and γ is the surface
tension of the liquid. Finally P is the excess pressure.
Method: the excess bubble pressure is measured using the apparatus shown in Figure 1.

Step 1; The tap should be open to the atmosphere. Open the clamp sufficiently to allow the rubber bulb to be filled
with air through the side valve. The liquid in the two tubes in the manometer should now be equal in height. Note
3
the manometric liquid is dibutyl phthalate which has a very small vapour pressure; its density is 1,046 g/cm at
o
20 C.
3
Now, fill the clean sample tube to /4 with double-distilled water, and place on the lab jack under the capillary
tube. The sample tube should be centrally placed. Raise the lab jack until the capillary just touches the surface of
the water (h = 0,00 cm).

Step 2; Close the tap, and open the main valve on the bulb and tighten the clamp sufficiently tight so that a bubble
forms at the end of the liquid. Measure the difference in height of the liquid (dibutyl phthalate) in the two
manometer arms. The excess pressure is given by

P = ∆hℓ®g (2)

Where ∆h is the difference in height ℓ®is the density of dibutyl phthalate.

Step 3; Open the tap, and loosen the clamp and refill the bulb by opening the side valve. Now raise the lab jack so
that the capillary dips into the liquid to a depth d. Use the capillary scale to determine this depth. (Note the scale is
not metric and must be calibrated using a metric metal rule and the conversion factor obtained at the end of the
experiment.)

Now repeat steps 1 and 2.

At least six measurements of d and h should be obtained.

Treatment of results

Use double-distilled water as the first liquid. From equations (1) and (2) we obtain

∆hℓ®g = dℓg + 2γ/r or ∆h = dℓ/ℓ® + 2γ/ ℓℓ®g (3)

Using (3), plot ∆h (y-axis) against d (x-axis ). The gradient as (ℓ/ℓ®) and the intercept on the ∆h axis is (2γ/rℓ®g).

Substitute for the γ value for water to obtain the constant (2/rℓ®g).

Repeat the method using the two unknown liquids. The constant, 2/rℓ®g obtained for water can now be used to
obtain γ from the intercept.

Precautions: 1. Ensure that the capillary is clean by placing the tip of it in a small sample bottle of acetone.
2. When changing the liquid ensure that the capillary tube tip is washed with liquid prior to measurement. Discard
this liquid and replace with fresh sample.

3. On no account should you allow liquid to be drawn up the capillary tube. This can be avoided by following
instructions carefully.

4. Do not touch the tip of the capillary tube as this will contaminate the tube with grease and affect your results.

EXPERIMENT 5: THE EMF`S AND USES OF CONCENTRATION CELLS AND THE

THERMODYNAMICS OF ELECTROCHEMICAL CELLS.

Objective:

To construct various concentration cells and measure their e.m.f.`s, and to deduce activity coefficients and
equilibrium constants from them.

Introduction

When two electrodes of the same chemical nature are combined to form a cell, an e.m.f. is produced if there is
some difference in the activity between two electrodes. Such a cell is called a concentration cell, and the
difference in activity may be brought about by having similar electrodes in contact with solutions of different ionic
activities.

As with any other electrochemical cell, the e.m.f. of the cell will be equal to the difference between the potentials
of the individual electrodes. The two electrodes may be conveniently connected by means of a salt bridge, which
usually consists of a glass tube containing a concentrated solution of a univalent electrolyte in which the transport
numbers of the cat ion and anion are very nearly equal. This has the consequence that the liquid junction potential
between the electrodes is approximately zero. In this experiment, the following typical concentration cell is
investigated (a1 anda2 are activities, and indicates a salt bridge):
 + +
Ag Ag , a1 Ag , a2 Ag ; a1 = γ1 c1 and a2 = γ2 c2

The equilibrium at a silver electrode is

+ -
Ag (aq) + e Ag(s)

And the potential, E2, of the right hand electrode in the above cell will be given by the Nernst equation as
Θ
E2 = EAg + RT/F x In a2 (1)
+
Where a2 is the activity of Ag ions in the electrode compartment.

The e.m.f, E, of the concentration cell is given by E = E2 – E1, E being positive or negative according to the
experimentally determined sign of the right-hand electrode, E2. Using equation (1),

E = RT/F x In a2/a1 (2)

If the activity in one electrode compartment is known then that in the other can be found. The second activity can
be controlled by a chemical equilibrium, hence enabling the equilibrium activities and constant to be found.

Also investigated here is the cell;

+ -
Ag Ag ; aAg+ Cl , aCl- AgCl Ag
-
where the right-hand electrode is a AgCl/Ag electrode, which is a reversible Cl electrode:
- -
AgCl(s) + e Ag(s) + Cl

Consequently the overall cell reaction is

+ -
AgCl(s) Ag (aq) + Cl (aq)

and its Nernst equation is

Θ -
E = E - (RT/F)In(aAg+)(aCl )
Θ
At equilibrium, E = 0, so E = (RT/F)InKsp

The measurement of cell e.m.f`s has a number of complications. Firstly the potential should be measured when
there is no current flowing: ideally a potentiometer is used, but an electronic voltmeter is also good. Secondly
there should be a state of equilibrium at the electrodes, and thirdly the electrode should be reversible – the rates
of the forwards and backwards electrode reactions should be high. Clean metal/ion electrodes can achieve the last
two conditions provided the ion activities are not determined by slow reactions.

Method
Prepare accurately using graduated flasks 0,005 and 0,001 mol/L silver nitrate solutions from the stock solution.
Next prepare the silver electrodes: rub gently with emery paper, dip them briefly in dilute nitric acid and then rinse
them with distilled water and store them in distilled water. Put them into a beaker containing some 0,01mol/L
silver nitrate solution and measure and record the cell potential and polarity. If it exceeds 0,005V obtain
replacement electrodes and check them.

Set up each of the following cells, rinsing silver electrodes with a little of their respective solutions first. Measure
their e.m.f`s and polarities: allow two minutes for equilibration and take three readings at one minute intervals. As
the sign displayed by the voltmeter belongs to the electrode connected to the Red/High/V terminal (sometimes
confusingly labeled +), this enables the polarity to be determined. Record the temperatures of the left-hand
electrodes.
+ +
1. Ag Ag , 0,01M Ag , a2 Ag with a2 for 0,005 and 0,001M solutions
+ -
2. Ag Ag , 0,01M Cl , 0,01M AgCl Ag. (Obtain the AgCl/Ag electrode from the technicians)
+ +
3. Ag Ag , 0,01M Ag , a2 Ag within the right-hand electrode compartment 0,01M KCl, to which is added
one drop of AgNO3.
+ +
4. Ag Ag , 0,01M Ag , a2 Ag within the right –hand electrode compartment a mixture of 25 ml of each
of 0,01M AgNO3 and 1,0 M NH3 solutions. Standardize the NH3 solution by diluting 25 ml to 250ml and titrating 25
ml aliquots with 0,1 M HCl solution using screened methyl orange.

Treatment of results

Where appropriate, correct the measured potentials for the zero-error of the silver electrodes, taking care to
+ -
account for the the polarities correctly. Use 0,892 and 0,902 as the activity coefficients of 0,01M Ag and Cl
respectively.
+
1) For each of the cell 1, deduce the ratio of the activities and of the activity coefficients for the Ag solutions, and
hence calculate the activity coefficients for 0,005 and 0,001 M solutions.
Θ
2) For cell 2 deduce E , and hence calculate Ksp for AgCl. Why is only one drop of silver nitrate solution required in
the right-hand compartment?

3) For cell 3 deduce a2 and hence Ksp for AgCl. By expressing E for each of the cells 2 and 3 in terms of Ksp.

4) For cell 4 deduce a2 and hence the equilibrium concentrations of the species and K for the formation constant
+
of the complex Ag (NH3)2 . Take the activity coefficient of the complex ion to be the same as that for the same
+
concentration of Ag about 0, 92.
EXPERIMENT 6: STUDY OF POTENTIOMETRIC AND INDICATOR END-POINTS

Discussion

The objectives of this experiment are to correlate electrometric and indicator end-points, to distinguish between
equivalence points and end-points and to investigate any indicator blanks and hence the choice of indicator.

The titration selected is that of phosphoric acid and sodium hydroxide. Phosphoric acid is a tribasic acid with three
successive ionizations:
- +
H3PO4 = H2PO 4 + H
- 2- +
H2PO4 = HPO4 + H
2- 3- +
HPO4 = PO4 + H

In this experiment three titrations of phosphoric acid with sodium hydroxide are carried out using three different
indicators. A fourth titration is performed, when the pH is recorded using a pH meter and a suitable glass and
calomel electrode assembly.

Apparatus and chemicals

3 3
Bench model pH meter, glass electrode, dip-type calomel electrode, 0, 2 mol/dm phosphoric acid, 0, 5 mol/dm
sodium hydroxide, methyl red, phenolphthalein and thymolphthalein indicators.

Method
3 3 3
10 cm of the phosphoric acid and 50 cm of distilled water are placed in a 250 cm conical flask and titrated with
sodium hydroxide to the methyl red end point. The titration is repeated using phenolphthalein and
3 3
thymolphthalein. Again 10 cm of the phosphoric acid are placed in a 250cm beaker and sufficient distilled water
added so that the glass and calomel electrodes are just covered. The electrodes are then connected to the pH
meter. A preliminary titration is then performed to determine the region where the pH changes most rapidly. In
subsequent titrations more frequent observations may then be made in these regions. The solution should be
stirred after each addition of alkali. Upon the completion of the titrations, the electrode system is immersed in
distilled water.

The results obtained are recorded in tabular form under the headings:

Volume of sodium hydroxide,V/cm pH ∆(pH)

∆V

Two graphs are plotted:

3
(a) pH Vs Vcm os sodium hydroxide
3
(b) ∆(pH)/∆V vs.V cm of sodium hydroxide ( use mid-point valuesof V)

The points of inflection on the first graph are correlated with the sharp peaks on the second graph. The volume of
sodium hydroxide is dertemined and the pH observed at the two equivalent points.

A table of indicators is consulted and by reference to their working range it is decided which indicator is preferable
for the titration of phosphoric acid solution to the first and second equivalence points. Indicator and electrometric
end points are compared and indicator blanks, if any are determined. It should be explained why only two
equivalence points are found in the titration of this tibasic acid.

The respective dissociation constants of phosphoric acid are:

+ -3
K1 = (H )H2PO4 = 7.54 x 10

(H3PO4)

+ 2- -6
K2 = (H )(HPO4 ) = 6.23 x 10
-
(H2PO4 )

+ 3- -13
K3 = (H )(PO4 ) = 4.79 x 10
2-
(HPO4 )
1. C.D Hodgman(Ed.) “Handbook of Chemistry and physics” Chemical Rubber Publishing Co.