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Department Of Biochemistry and Medical Chemistry

Medical School, University of Pcs

Qualitative chemical analysis


from

LABORATORY EXPERIMENTS
IN MEDICAL CHEMISTRY

Edited by
GYRGY OSZBACH

PCS, 1995

CONTENTS

1. INTRODUCTION

Laboratory safety..................................................................................................... 3
Accident protection, fire protection, first aid .......................................................... 5
2. LABORATORY UTENSILS AND METHODS

Utensils.................................................................................................................... 9
Simple laboratory methods...................................................................................... 9
Laboratory measurements .................................................................................. 9
Heating ............................................................................................................... 9
Forming precipitates ........................................................................................ 12
Preparation of gases......................................................................................... 12
3. SIMPLE LABORATORY SEPARATION METHODS

14

Decantation............................................................................................................ 14
Filtration ................................................................................................................ 14
Drying.................................................................................................................... 15
4. CHEMICAL ANALYSIS

17

4.1 QUALITATIVE CHEMICAL ANALYSIS .......................................................... 18


Detection of cations............................................................................................... 19
Detection of anions................................................................................................ 32
Simple analysis of cations and anions ................................................................... 39
Self-test questions ................................................................................................. 42
9. APPENDIX

44

9.1 INORGANIC CHEMISTRY; A short overview................................................... 44


Classification of the inorganic compounds ........................................................... 45
The nomenclature of the inorganic compounds .................................................... 51
Solubility of inorganic compounds in water ......................................................... 55
9.3 CONCENTRATIONS OF REAGENT SOLUTIONS .......................................... 56

INDEX OF LABORATORY EXPERIMENTS

2. LABORATORY UTENSILS AND METHODS


2.1 Preparation of a solution of a given concentration.................................................12
2.2 Preparation of capillary tubes.................................................................................15
3. SIMPLE LABORATORY SEPARATION METHODS
4. CHEMICAL ANALYSIS
4.1 QUALITATIVE CHEMICAL ANALYSIS
Detection of cations
4.1.1-5
Reactions of lead(II) ion.............................................................................34
4.1.6-9
Reactions of mercury(I) ion........................................................................35
4.1.10-13 Reactions of mercury(II) ion ......................................................................36
4.1.14-18 Reactions of copper(II) ion.........................................................................37
4.1.19-21 Reactions of arsenic(III) ion .......................................................................38
4.1.22-25 Reactions of cobalt(II) ion..........................................................................40
4.1.26-28 Reactions of chromium(III) ion..................................................................41
4.1.29-33 Reactions of zinc ion ..................................................................................42
4.1.34-36 Reactions of iron(II) ion .............................................................................43
4.1.37-40 Reactions of iron(III) ion............................................................................44
4.1.41-43 Reactions of calcium ion ............................................................................45
4.1.44-46 Reactions of magnesium ion ......................................................................46
4.1.47-48 Reactions of sodium ion.............................................................................47
4.1.49-51 Reactions of potassium ion ........................................................................47
4.1.52-54 Reactions of ammonium ion ......................................................................48
4.1.55-56 Reactions of hydrogen ion..........................................................................49
Detection of anions
4.1.57-59 Reactions of carbonate ion .........................................................................51
4.1.60-61 Reactions of hydrogen carbonate ion .........................................................52
4.1.62

Reaction of hypochlorite ion ......................................................................52

4.1.63
Reaction of sulphate ion.............................................................................53
4.1.64-66 Reactions of phosphate ion ........................................................................53
4.1.67

Reactions of chloride ion............................................................................54

4.1.68-70 Reactions of iodide ion...............................................................................55


4.1.71-72 Reactions of nitrite ion ...............................................................................56
4.1.73-74 Reactions of nitrate ion ..............................................................................57
4.1.75
Reactions of hydroxide ion ........................................................................57
4.1.76

Simple analysis of cations and anions........................................................58

PREFACE

ince the English Program started at the University Medical School of Pcs in
1984, remarkable changes have been made in chemical education. Today,
there are appropriate textbooks available to support the lectures and seminars
in the fields of General, Organic and Bioinorganic Chemistry. In 1994, the
Department issued a handout on Inorganic Chemistry, but there was a lack of an
updated laboratory manual. (The former one was written in 1984 and the last reprint
was edited in 1991.) This edition is a translation of the Hungarian version ("Orvosi
kmiai gyakorlatok") issued this year.
The manual contains experiments much more than can be completed within
the limited time of the main course. Among them, there are practices to be replaced in
the future by another ones that cannot be performed for the time being. Some of the
experiments, mainly the instrumental ones, appear as demonstrations, which are
planned to be carried out by the students themselves.
When writing the lab manual, our main object was to enable students to work
independently in the laboratory, observe relevant phenomena, draw conclusions and
make notes, by which anyone can reproduce the experiment.
It is strongly recommended, that students carefully study Chapter 1,
"Laboratory Safety", before starting work in the laboratory to avoid accidents.
Chapter 2 ("Laboratory Utensils and Methods") and 3 ("Simple Laboratory
Separation Methods") comprise general laboratory methodology, which are to be
mastered so that it can provide a firm knowledge throughout the course. The
following "Chemical Analysis" section includes qualitative, quantitative, organic and
bio-organic analytical practices. In Chapter 5 ("Reaction Kinetics") and Chapter 6
("Chemical Equilibria") simple test-tube reactions help students comprehend the basic
concepts of the processes also important in life sciences. A separate chapter, number
7, is devoted to the most powerful separation method, chromatography, widely used in
biomedical practice and research. Chapter 8, "Instrumental Analysis", offers an insight
into the high-performance methods employed in modern diagnostic laboratories.
In Chapter 9 (Appendix) one can find an overview of Inorganic Chemistry,
particularly recommended in the first half of the course. Calculation Exercises are
attached to promote student's own preparation for the exams on General Chemistry.
Concentrations of reagent solutions used regularly in the practices, which are
prepared by technicians in the stock laboratory, are not indicated in the text. For a
better reproducibility, they are also available in the Appendix.

Our special appreciation is extended to Miss Andrea Gungl and Mrs va


Halsz for the preparation of figures, and to Mrs Gabriella Nmeth for the computeredited structural formulas.
Despite multiple painstaking revisions, there must have some misprints and
other errors left in the manual. Notices on correction and improvement are thankfully
welcome.
21 May 1995
The Editor

1. INTRODUCTION
LABORATORY SAFETY

When working in a chemical laboratory we are handling several chemicals


with more or less adverse effects to human health, and we are performing experiments
that have a number of potential hazards associated with them. Thus, a chemical
laboratory can be a dangerous place to work in. With proper care and circumspection,
strictly following all precautionary measures, however, practically all accidents can be
prevented.
It is the prevention of accidents and damages posed by the speciality of the
chemical laboratory experiments that requires you to follow the instructor's advice as
well as keep the laboratory order during work in the laboratory. You should never
forget that your carelessness or negligence can threaten not only your own safety but
that of your classmates working around you.
This section has guidelines that are essential to perform your experiments in a
safe way without accident.

Preparation in advance
a) Read through the descriptions of the experiments carefully. If necessary, do
study the theoretical background of the experiments from your chemistry book(s).
After understanding, write down the outline of the experiments to be performed in
your laboratory notebook. If any items you don't understand remain, do ask your
instructor before starting work.
b) Prepare your notebook before the laboratory practice. Besides description of
the outline of the experiments, preliminary preparation should also include a list of the
chemicals and procedures which need special care and attention to avoid laboratory
accidents during your work.

Laboratory rules
a) The laboratory instructor is the first to enter and the last to leave the
laboratory. Before the instructor's arrival students must not enter the laboratory.

b) Always wear laboratory coat and shoes in the laboratory. Sandals and opentoed shoes offer inadequate protection against spilled chemicals or broken glass.
c) Always maintain a disciplined attitude in the laboratory. Careless acts are
strictly prohibited. Most of the serious accidents are due to carelessness and
negligence.
d) Never undertake any unauthorized experiment or variations of those
described in the laboratory manual.
e) Maintain an orderly, clean laboratory desk and cabinet. Immediately clean
up all chemical spills from the bench and wipe them off the outer wall of the reagent
bottles with a dry cloth.
f) Smoking, drinking, or eating is not permitted during the laboratory practice.
Do not bring other belongings than your notebook, stationery, and laboratory manual
into the laboratory. Other properties should be placed into the locker at the corridor.
g) Be aware of your neighbour's activities. If necessary, warn them of improper
techniques or unsafe practices.
h) At the end of the lab, completely clean all glassware used in the
experiments, clear the laboratory bench of reagent bottles, glassware and equipment,
and clean it with a dry cloth. After putting back all your personal labware into your
cabinet, lock it carefully.
i) Always wash your hands with soap before leaving the laboratory.

Handling chemicals and glassware


a) At the beginning of the laboratory practices the instructor holds a short
introduction when all questions related to the experimental procedures can be
discussed.
b) Perform each experiment alone. During your work always keep your
laboratory notebook nearby in order to record the results of the experiments you
actually perform.
c) Handle all chemicals used in the experiments with great care. Never taste,
smell, or touch a chemical or solution unless specifically directed to do so.
d) Avoid direct contact with all chemicals. Hands contaminated with
potentially harmful chemicals may cause severe eye or skin irritations.

e) Reactions involving strong acids, strong bases, or chemicals with


unpleasant odour should be performed under the ventilating hood. If necessary, safety
glasses or goggles should be worn.
f) When checking the odour of a substance, be careful not to inhale very much
of the material. Never hold your nose directly over the container and inhale deeply.
g) When carrying out the experiments, first read the label on the bottle twice to
be sure of using the correct reagent. The wrong reagent can lead to accidents or
"inexplicable" results in your experiments.
h) Do not use a larger amount of reagents than the experiment calls for. Do not
return any reagent to a reagent bottle. There is always the chance that you accidentally
pour back some foreign substance which may react with the chemical in the bottle in
an explosive manner.
i) Do not insert your own pipette, glass rod, or spatula into the reagent bottles;
you may introduce impurities which could spoil the experiment for the person using
the stock reagent after you.
j) Mix reagents always slowly. Pour concentrated solutions slowly and
continuously stirring into water or into a less concentrated solutions. This is especially
important when diluting concentrated sulphuric acid.
k) Discard waste or excess chemicals as directed by your laboratory instructor.
The sink is not for the disposal of everything.
l) Using clean glassware is the basic requirement of any laboratory work.
Clean all glassware with a test-tube brush and a detergent, using tap water. Rinse first
with tap water and then with distilled water. If dry glassware is needed, dry the wet
one in drying oven, or rinse with acetone and air dry it.

ACCIDENT PROTECTION, FIRE PROTECTION AND FIRST AID

Accident and fire protection


a) Before starting the experiments make sure all the glassware are intact. Do
not use cracked or broken glassware. If a glassware breaks during the experiment, the
chemical spill and the glass splinters should be cleaned up immediately. Damaged
glassware should be replaced from the stock laboratory.
b) Fill not more than 4-5 cm3 of reagent into a test tube. As you are
performing the experiments, do not look into the mouth of the test tube and do not

point it at anyone. If you want to check the odour of a substance formed in a test tube
reaction, waft the vapours from the mouth of the test tube toward you with your hand.
c) Before heating glassware make sure that its outer wall is dry. Wet glassware
can easily break on heating. When heating liquids in a test tube, hold it with a piece of
tightly folded paper or a test-tube holder.
d) When heating liquids in an Erlenmeyer flask or in a beaker, support the
glassware on a wire gauze placed on an iron tripod, and put a piece of boiling stone
into the liquid to prevent bumping. Start heating with a law flame and intensify it
gradually.
e) When lighting the Bunsen burner, close the air-intake holes at the base of
the burner, open the gas cock of the outlet, and bring a lighted match to the mouth of
the burner tube until the escaping gas at the top ignites. (It is advantageous to strike
the mach first and then open the gas cock.) After it ignites, adjust the air control until
the flame is pale blue and the burner produces a slight buzzing sound.
f) If the Bunsen burner "burns in", which can be noticed from its green flame
and whistling (whizzing) sound, the gas valve of the outlet should be turned off
immediately. Allow the burner to cool, and light it again as described above.
g) When using an electric heater or other electric device, do not touch them
with wet hands and prevent liquids from spilling over them. If it accidentally happens
(e.g. a flask cracks on heating), unplug the device immediately and wipe off the liquid
with a dry cloth.
h) As a general rule, a flame should be used to heat only aqueous solutions.
Most organic solvents boil below the boiling point of water. A hot water bath can be
effectively used to heat these solvents.
i) When working with flammable organic solvents (e.g. hexane, diethyl ether,
petroleum ether, benzene) use of any open flame in the laboratory is prohibited. The
vapours of the flammable substances may waft for some distance down their source;
thus presenting fire danger practically in the whole laboratory.
j) In case of a smaller fire (e.g. a few millilitres of organic solvent burning in a
beaker or an Erlenmeyer flask), it can be extinguished by placing a watch glass over
the mouth of the flask. In case of a bigger fire and more serious danger, use the fire
extinguisher fixed on the wall of the laboratory. At the same time alarm the University
Fire Fighter Office by calling the N 1333 from the corridor or from the stock lab.
k) Never blow the fire. This way you might turn the fire up and the flame can
shoot into your face. Do not use water to smother fires caused by water-immiscible

chemicals (e.g. benzene) and alkali metals. Pouring water on a plugged electric device
is also prohibited.
l) If your clothing catches fire, you can smother the flames by wrapping
yourself in a wet towel or a laboratory coat.
m) In case of fire in the laboratory the main gas valve and the electric switch
of the laboratory should be turned off immediately. (They are located in the corridor
on the outer wall of the laboratory.) Besides fighting the fire, start giving the injured
first aid immediately.

First aid
a) In case of an accident or injury, even if it is minor, notify your laboratory
instructor at once. The urgent first aid is an absolute requirement for the prevention of
more serious adverse health effects.
b) Minor burns caused by flames or contact with hot objects should be cooled
immediately by flooding the burned area with cold water, then treating it with an
ointment. Severe burns must be examined by a physician.
c) In case of a cut, remove the contamination and the glass splinters from the
wound. Disinfect its boundary with alcoholic iodine solution and bind it up with
sterile gauze. In case of severe cases the wound should be examined and treated by a
physician.
d) Whenever your skin gets into contact with chemicals, wash it quickly and
thoroughly with water. In case of chemical burns, the chemical should be neutralized.
For acid burns, the application of a dilute sodium hydrogen carbonate, for burns by
alkali, the application of a dilute solution of boric acid is used. After neutralization,
wash the affected area with water for 5-10 minutes and apply an oily ointment if
necessary.
e) Concentrated sulphuric acid dripped onto your skin must be wiped away
with a dry cloth. Then the affected area should be treated as described for acid burns
above.
f) Acids splashed onto your clothes could be neutralized with diluted solution
of ammonia or sodium hydrogen carbonate.
g) If any chemical gets into your mouth, spit it out immediately, and wash your
mouth well with water. In case of acidic or basic chemicals rinse your mouth first with
a diluted solution of sodium hydrogen carbonate or that of boric acid, respectively, to
neutralize the acid or the base.
7

h) If any chemical enters your eyes, immediately irrigate the eyes with large
quantities of water. In case of any kind of eye damage consult a physician
immediately.
i) In case of inhalation of toxic chemicals the injured should be taken out to
fresh air as soon as possible.
j) In case of an electric shock, the immediate cutoff of the electric current
supply of the laboratory (main switch) is the most important step to avoid irreversible
health damage. The injured should get medical attention as soon as possible. If
necessary, artificial respiration should be given until the physician arrives.

2. LABORATORY UTENSILS AND METHODS

UTENSILS

The most common laboratory utensils are shown in Fig. 2.1a-b

SIMPLE LABORATORY METHODS

Laboratory Measurements

Concerning basic laboratory measurements (weighing, measuring volume,


temperature, density, etc.) and data processing we refer to Biophysics and Biometrics.

Heating

In the laboratories, both direct and indirect methods of heating are used. For
direct heating a free gas flame or an electric hotplate or an electric heating mantle, for
indirect heating mostly liquid baths (water, mineral oil, silicone oil, glycerol) are used.
One of the most common sources of heat is the gas Bunsen burner (Fig.2.1b).
Solid materials can be heated (or ignited) on a direct flame in porcelain or
metal crucibles placed onto an iron tripod by means of a clay triangle. Heating is
started with a small flame and intensified gradually. Ignitions under precisely
controlled conditions can also be performed in an electric furnace.
Smaller amounts of aqueous solutions may be heated and boiled on direct
flame keeping a test tube with not more than 3-4 cm3 of the solution into the mantle
of the flame by means of a strip of a triple-folded paper sheet or a test-tube holder.
First the upper part of the solution is heated and then the rest. Caution: Never turn the
opening of a heated test tube toward your face or toward other people working
nearby.
Larger amounts of nonflammable, not too volatile liquids can be heated and
boiled in an Erlenmeyer flask or a beaker placed onto an iron tripod by means of an

asbestos wire gauze. In case of boiling, a piece of pumice (boiling stone) is placed into
the solution to avoid bumping.

Fig. 2.1a; Laboratory utensils


10

1. Test tube

Fig.1b; Laboratory utensils


2. Conical (Erlenmeyer) flask

3. Beaker

4. Wash bottle

5. Measuring cylinder

6. Glass funnel

7. Watchglass

8. Porcelain crucible

9. Petri dish
11.Narrow-mouthed reagent bottle

10. Wide-mouthed reagent bottle


12. Glass rod

13. Crucible tongue

14. Plastic spoon

15. Bunsen burner

16. Asbestos wire gauze

17. Clay triangle

18. Porcelain dish

11

Flammable liquids in a smaller amount can be heated on an electric hotplate


or in a water bath under the hood. Larger amounts of flammable liquids should be
heated and boiled in flasks equipped with a reflux condenser (Fig. 3.8) by a suitable
liquid bath or an electric heating mantle.

Forming Precipitates

Precipitates are produced mostly for analytical purposes. Then the visual observation
is very important. Therefore, the reagent is added gradually with shaking while the
changes are monitored. For a complete precipitation, the reagent should be added in
excess. Note that in case of amphotery or complex formation the excess of the reagent
can dissolve the previously formed precipitate.

Preparation of Gases

Laboratory gases (O2, N2, Cl2, H2, CO2, N2O, HCl, noble gases) on large scale are
put on the market in high-pressure cylinders. Smaller amounts of them can also be
prepared in the laboratory. The most widely used gas generator is the so-called Kipp's
apparatus which is suitable for producing gases from a solid, water-insoluble and a
liquid reactant (Fig. 2.2). It consists of two bulbs separated by a diaphragm and of a
long-stem funnel introducing the solution into the lower bulb. The apparatus functions
semi-automatically as follows:

Fig. 2.2; Kipp's apparatus

12

The solid reactant is placed into the middle bulb and, from the upper funnel,
the liquid reactant is introduced into the lowest bulb. The lowest bulb can not be filled
because of the resistance of the compressed air in the two lower bulbs. Turning the
gas-outlet stopcock on, the hydrostatic pressure pushes the liquid reactant through the
diaphragm into the middle part and the reaction starts. If the gas cock is turned off, the
increasing pressure of the evolving gas presses the liquid back into the lowest part and
the reaction is stopped. However, the apparatus is then ready to function again if the
cock is turned on. Usually a wash bottle is attached to the gas outlet for washing out
the drops of the reagents and for flow control. A rate of not more than 2 to 3 bubbles
per second gas flow is advised.
Gases frequently prepared in Kipp's apparatus:
Hydrogen from granulated zinc and hydrochloric acid according to the equation:
Zn + 2 H+ = H2 + Zn2+
Hydrogen sulphide from iron(II) sulphide and hydrochloric acid:
FeS + 2 H+ = H2S + Fe2+
Carbon dioxide from cracked marble and hydrochloric acid:
CaCO3 + 2 H+ = Ca2+ + H2O + CO2

13

3. SIMPLE LABORATORY SEPARATION METHODS

Decantation

The simplest way of the separation of a liquid from a solid phase is called decantation.
In this operation a suspension is allowed to stand until the precipitate settles down and
then the supernatant liquid is cautiously poured off. Then, the rest is suspended in
distilled water and the procedure is usually repeated twice to remove the dissolved and
adsorbed impurities. For the sedimentation of very fine suspensions, especially for
that of colloidal ones, centrifugation is used.

Filtration

Filtration means the separation of two phases with the aid of a filtering layer which
allows only one of the phases to pass through. Usually the solid phase is separated
from the liquid and rarely from the gaseous phase. In case of simple filtration,
hydrostatic pressure is enough to have the liquid pass through. To enhance the rate of
filtration, reduced pressure can be applied for vacuum filtration in the laboratory.
Rarely, filtration under pressure is also applied.
If simple filtration is performed at atmospheric pressure, smooth, conical and
short-stem funnels are used (Fig. 3.1).

Fig. 3.1; Glass funnels

14

Drying

Drying means the removal of an unnecessary liquid or its vapour from a solid, liquid
or gaseous material. In most cases, water is to be removed. The performance of drying
depends on the state of matter and the thermal stability of the substance to be dried.
Thus, gases and liquids are usually kept in direct contact with the drying agent. Solid
samples are usually placed into a closed space (desiccator) and the drying agent acts
through the common airspace (Fig. 3.6). A wide variety of hygroscopic materials are
used as dehydrating agents. Of hydrate-forming substances, anhydrous CaCl2,
Mg(ClO4)2, Na2SO4, K2CO3 cc. H2SO4, NaOH and KOH are widely used. Some
metals and a few oxides bind water by a chemical reaction, e.g. Na, K, CaO, P2O5.
Silica gel, which is coloured by a blue cobalt salt when prepared for drying, binds
water by adsorption. If silica is saturated with water, the blue colour of the cobalt salt
turns pink, indicating that silica should be reactivated by warming.

Fig. 3.6; Desiccator; infrared lamp

Solids, at room temperature, are dried in a desiccator (Fig 3.6). The


dehydrating agent is placed at the bottom of the apparatus, and the substance to be
dried onto the perforated plate. Reduced pressure may be applied to increase the
evaporation rate (vacuum desiccator). Thermally stable samples may be dried in an
electric oven or under an infrared lamp (Fig. 3.6).
15

Gases can be dried by passing them through an adsorption tube with a solid
packing, e.g. P2O5 or silica or through a washing bottle filled with a liquid drying
agent, e.g. cc. sulphuric acid.
Liquids are usually dried by adding an insoluble solid dehydrating agent and
are allowed to stand for a longer period of time. The drying agent can be removed by
filtration or decantation. For the dehydration of certain organic solvents, azeotropic
distillation (see later, at "Distillation") is useful.
Demonstration: Desiccator, infrared lamp.

16

4. CHEMICAL ANALYSIS

The aim of chemical analysis is the qualitative recognition and the determination of
the quantity of the constituents (e.g. atoms, ions, groups) of substances or mixtures.
Accordingly, analytical chemistry can be classified into two main parts: qualitative
and quantitative analysis. However, in the modern natural science and industry it is
also requested to answer questions about the form, distribution and interactions of the
constituents. Therefore, the task of analysis is to answer all the questions about the
chemical composition, structures, etc. being important in the characterization or
usage.
Chemical analysis may be classified according to the nature of the substances
investigated. Thus, inorganic and organic analysis are different but not strictly
independent fields of analysis. Inorganic analysis may be subdivided into metal,
silicate, etc. analysis; organic analysis comprises hydrocarbon, protein, food,
pharmaceutical, etc. analysis.
Another way of classification is based on the applied methods. The two main
branches of quantitative analysis are gravimetry and titrimetry. Gravimetry is based on
the measurement of the mass of the samples, while the volumetric methods are based
on the measurement of volumes proportional with the amount of a gas or a dissolved
reactant. Many of the physical or physicochemical properties are known to give
measurable values proportional with the mass or the concentration of different
samples. These instrumental analysis methods allow to perform the gravimetric or
volumetric determinations more precisely and sometimes can be automated. On the
other hand, instrumental methods themselves are useful to determine concentration or
composition occasionally together with structure. Separation methods represent
another enormously developing field of analysis.
It should be noted that the modern, fast and high performance methods unify
the separation, detection and quantitative determination techniques as well. The
principles are the following:
a) During separation the components are identified and usually quantitatively
measured. (E.g. immunoelectrophoresis, affinity chromatography or the combined gas
chromatography-mass spectrometry in which the chromatographically separated and
quantitatively measured
spectrometer.)

components are identified by the attached mass

17

b) Without separation, selective analysis methods are used for one or more
components of a mixture not being sensitive to other components present (e.g.
enzymatic determination of blood glucose).

18

4.1 QUALITATIVE CHEMICAL ANALYSIS

Qualitative analysis deals with the identification of elements and compounds


respectively, with the detection of individual components in their mixtures. Often
from the physical properties some conclusion may be drawn about the quality. Thus,
density, melting point, boiling point, colour, odour, etc. may carry partial information.
Since reliable conclusion, as regards the composition, can be drawn only from
chemical behaviour, the chemical reactions of a sample should be studied. Various
reagents should be added and the physical-chemical changes observed. The reactions
should be rapid, sensitive and selective.
Most of the reactions are carried out in aqueous solutions and the observable
changes are as follows:
a) The reagent reacts with one or more components of the sample forming an
insoluble precipitate. Further information can be drawn from the colour of the
precipitate and its behaviour against other reagents.
b) In other cases the reaction is accompanied with gas evolution. Then, the
physical-chemical properties of the gas may be informative.
c) The reagent brings about a colour-change in the solution.
d) Certain substances placed into gas flame change its colour (flame test).
Depending on the amounts of the samples and the expenses, test-tube, spot
and microchemical reactions can be carried out. Test-tube reactions are performed
with 1-2 cm3 of the sample in test tubes. The reagent is added dropwise with shaking,
occasionally with gentle heating. Spot reactions mean using 1-2 drops of the reactants
on a watch-glass, a porcelain dish or a filter paper. Microchemical reactions are
carried out under a microscope with very little amounts.

19

DETECTION OF CATIONS

During the systematic qualitative analysis the test for cations always precedes
that of anions since the previous knowledge of the present cations simplifies the
analysis of anions.
The most common cations are classified into five analytical groups taking
advantage of the different solubility of their derivatives formed with the reagents
added subsequently in the order: hydrochloric acid, hydrogen sulphide, ammonium
sulphide and ammonium carbonate. The formulas of physiologically important
(essential or poisonous) ions are underlined. They will be studied in the laboratory
course.

To Group 1 belong cations which form a precipitate with hydrogen sulphide


in nitric acid solution, and the sulphide is insoluble in ammonium sulphide. The
group is subdivided into two subgroups according to the solubility of their chlorides.
Members of Group 1a give a precipitate with hydrochloric acid: Ag+, Pb2+, Hg22+.
Chlorides of cations of Group 1b are soluble in water. To this group Hg2+, Cu2+,
Bi3+, Cd2+ belong.
Group 2 consists of cations forming insoluble sulphides with hydrogen
sulphide in nitric acid solution. However, these sulphides are soluble in ammonium
sulphide in form of thio salts: As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+.
Group-3 cations form insoluble sulphides only in neutral or slightly basic
medium with ammonium sulphide. These sulphides are soluble in dilute hydrochloric
acid: Co2+, Ni2+, Fe2+, Fe3+, Cr3+, Al3+, Zn2+, Mn2+.
Group-4 cations do not react with the above reagents. They form insoluble
carbonate precipitate with ammonium carbonate in a neutral medium: Ca2+, Sr2+,
Ba2+.
Group-5 cations have no group reactions. They have to be detected with
specific reactions: Mg2+, Na+, K+, NH4+, Li+, H+.

20

GROUP 1a

Reactions of mercury(I) ion (Hg22+)

For testing the reactions of mercury(I) ion, mercury(I) nitrate [Hg2(NO3)2]


stock solution is used.

Experiment 4.1.6 (Subgroup reaction)


a) Addition of HCl solution leads to the formation of white crystals of
mercury(I) chloride (calomel).
Hg22+ + 2 Cl- = Hg2Cl2
b) Adding NH4OH solution to the crystals, elementary mercury and mercury
amido chloride form (disproportionation) and the slurry turns grey.
Hg2Cl2 + NH4+ + 2 OH- = Hg

Cl
NH2

+ Hg + Cl- + 2 H2O

Experiment 4.1.7 (Group reaction)


On the action of H2S gas, mercury(I) ions disproportionate to form a black
precipitate of elementary mercury and mercury(II) sulphide. The precipitate is
insoluble in acids.
Hg22+ + S2- = Hg + HgS

Experiment 4.1.8
Adding NaOH solution, black mercury(I) oxide precipitates.
Hg22+ + 2 OH- = Hg2O + H2O

Experiment 4.1.9
Adding NH4OH solution, metallic mercury and basic mercury(II) amido
nitrate form as a black precipitate (disproportionation).

21

2 Hg22+ + NO3- + NH4+ + 4 OH- = HgO Hg

NH2
NO 3

+ 2 Hg + 3 H2O

GROUP 1b

Reactions of mercury(II) ion (Hg2+)

For testing the reactions of mercury(II) ion, mercury(II) chloride [HgCl2]


stock solution is used.

Experiment 4.1.10 (Group reaction)


Introducing H2S gas into an acidic mercury(II) solution, a black precipitate of
mercury(II) sulphide deposits.
Hg2+ + S2-= HgS

Experiment 4.1.11
NaOH solution precipitates yellow mercury(II) oxide. Difference from
mercury(I) ion which turns black with NaOH.
Hg2+ + 2 OH- = HgO + H2O

Experiment 4.1.12
NH4OH solution precipitates white mercury(II) amido chloride.
Hg2+ + Cl- + NH4+ + 2 OH- = Hg

NH2
Cl

+ 2 H2 O

Experiment 4.1.13
Potassium iodide (KI) solution gives a red precipitate of mercury(II) iodide.
The precipitate dissolves in excess reagent to form colourless, water-soluble
tetraiodomercurate(II) ion.
Hg2+ + 2 I- = HgI2

22

HgI2 + 2 I- = [HgI4]2The alkaline solution of the complex salt is the so-called Nessler's reagent, which is
used for testing NH4+.

GROUP 2.

Reactions of arsenic(III) ion (As3+)

For testing the reactions of arsenic(III) ion, arsenic trioxide [As2O3] stock solution is
used.

Experiment 4.1.19 (Group reaction)


From a solution acidified with HCl (!), H2S gas precipitates yellow arsenic(III)
sulphide ( if necessary, gentle warming is possible).
As2O3 + 6 H+
2 As3+ + 3 H2O
2 As3+ + 3 S2- = As2S3
The precipitate dissolves in excess (NH4)2S solution forming a colourless
solution of ammonium thioarsenite. (Difference from Group 1.)
As2S3 + 3 S2- = 2 AsS33-

Experiment 4.1.20
Bettendorf's test:
Bettendorf's reagent, tin(II) chloride (SnCl2) in cc. HCl solution (caution, very
caustic!), reduces arsenic compounds to elementary arsenic as a black precipitate or a
mirror on the wall of the test tube.
2 As3+ + 3 Sn2+ = 2 As + 3 Sn4+
Procedure:
Excess volume of Bettendorf's reagent is added to the test solution and is
allowed to stand for a few minutes.

23

Experiment 4.1.21
Gutzeit's test:
Elementary zinc (in hydrochloric acid medium) reduces the soluble arsenic
compounds to arsine gas (AsH3). Allowing the gas to come into contact with a filter
paper wetted with a drop of concentrated silver nitrate solution, a yellow spot appears
which turns black when applying a drop of water onto it.
AsO33- + 9 H+ + 3 Zn = AsH3 + 3 Zn2+ 3 H2O
AsH3 + 6 AgNO3 = Ag3As . 3 AgNO3 + 3 HNO3
Ag3As . 3 AgNO3 + 3 H2O = 6 Ag + H3AsO3 + 3 HNO3

Procedure:
To 1 cm3 As-containing solution a few cm3s of HCl, a few drops of CuSO4
and a piece of zinc metal are added. A wad of cotton wool is applied into the mouth of
the test tube as a filter and the tube is covered with a piece of filter paper wetted with
a drop of 50 % silver nitrate. A yellow spot develops within a few minutes which
turns black when a drop of water is added.

24

GROUP 3

Reactions of iron(II) ion (Fe2+)

For testing the reactions of iron(II) ion, iron(II) sulphate [FeSO4] stock
solution is used.

Experiment 4.1.34 (Group reaction)


From a neutral solution, (NH4)2S solution precipitates black iron(II) sulphide
which is soluble in HCl.
Fe2+ + S2- = FeS
FeS + 2 H+ = Fe2+ + H2S

Experiment 4.1.35
NaOH solution precipitates greenish-white iron(II) hydroxide, which, allowed
to stand on air, is oxidized to brown iron(III) hydroxide.
Fe2+ + 2 OH- = Fe(OH)2
4 Fe(OH)2 + 2 H2O + O2 = 4 Fe(OH)3

Experiment 4.1.36
K3[Fe(CN)6], potassium-hexacyanoferrate(III) solution precipitates dark blue
iron(II) hexacyanoferrate(III).
3 Fe2+ + 2 [Fe(CN)6]3- = Fe3[Fe(CN)6]2

25

Reactions of iron(III) ion (Fe3+)

For testing the reactions of iron(III) ion, iron(III) chloride [FeCl3] stock
solution is used.

Experiment 4.1.37 (Group reaction)


From a neutral solution, (NH4)2S solution precipitates black iron(II) sulphide
and elementary sulphur.
2 Fe3+ + S2- = 2 Fe2+ S
Fe2+ + S2- = FeS
HCl dissolves FeS, and the milky colloidal dispersion of sulphur can be seen.

Experiment 4.1.38
NaOH solution deposits reddish-brown, gelatinous iron(III) hydroxide.
Fe3+ + 3 OH- = Fe(OH)3

Experiment 4.1.39
K4[Fe(CN)6], potassium hexacyanoferrate(II) solution precipitates iron(III)
hexacyanoferrate(II) (Prussian blue). The reaction is specific for Fe3+ ion.
4 Fe3+ + 3 [Fe(CN)6]4- = Fe4[Fe(CN)6]3

Experiment 4.1.40
NH4SCN, ammonium thiocyanate (ammonium rodanide) solution in slightly
acidic medium produces blood-red coloration. Iron(III) thiocyanate formed may be
extracted (transferred into another phase) by shaking with diethyl ether.
Fe3+ + 3 SCN- = Fe(SCN)3

26

GROUP 4

Reactions of calcium ion (Ca2+)

For testing the reactions of calcium ion, calcium chloride [CaCl2] stock
solution is used.

Experiment 4.1.41 (Group reaction)


(NH4)2CO3 or Na2CO3 solution in neutral or slightly alkaline medium
precipitates white crystals of calcium carbonate.
Ca2+ + CO32- = CaCO3

Experiment 4.1.42
(NH4)2(COO)2, ammonium oxalate solution in slightly basic, neutral or acetic
acid medium precipitates white Ca oxalate. This reaction is characteristic and very
sensitive to Ca2+ ion.
Ca2+ + (COO)22- = Ca(COO)2

Experiment 4.1.43

Fig. 4.1.1; Flame test

27

Flame test. The volatile Ca compounds colour the gas flame brick-red.
General procedure:
Into a porcelain crucible, 1 cm3 of the sample solution (or 0.1-0.5 g of a solid
sample) and a granule of elementary zinc are placed and the crucible is almost totally
filled with 20 % hydrochloric acid solution. The non-luminous flame of the Bunsen
burner held horizontally above the intensively bubbling solution changes its colour
(Fig. 4.1.1).

GROUP 5

Reactions of magnesium ion (Mg2+)

Magnesium ion belongs to Group 5, since, in the presence of other ammonium


salts, it does not form a precipitate with (NH4)2CO3.

For testing the reactions of magnesium ion, magnesium chloride [MgCl2]


stock solution is used.

Experiment 4.1.44
NaOH solution precipitates white, gelatinous magnesium hydroxide.
Mg2+ + 2 OH- = Mg(OH)2
In the presence of ammonium salts, due to the decrease of OH- concentration, the
precipitate does not form (see mass-action law; solubility product and Exps. 4.1.65
and 6.10).

Experiment 4.1.45
In the absence of other ammonium salts, (NH4)2CO3 or Na2CO3 solution
precipitates white crystals of basic magnesium carbonate.
4 Mg2+ + 4 CO32- + 4 H2O = Mg(OH)2.3 MgCO3.3 H2O + CO2

28

Experiment 4.1.46
Magnesia mixture (see Exp. 4.1.65 and Exp. 6.10) forms a white precipitate
with sodium hydrogen phosphate (a characteristic reaction of both magnesium and
phosphate ions).
Mg2+ + NH4+ + PO43- = MgNH4PO4
Reactions of sodium ion (Na+)

For testing the reactions of sodium ion, sodium chloride [NaCl] stock solution
is used.

Experiment 4.1.47
Flame test: (For the performance see Exp. 4.1.43.) Sodium chloride vapour
colours the flame intense yellow (very sensitive for sodium).

Experiment 4.1.48
In a neutral or slightly alkaline medium potassium hexahydroxoantimonate(V)
solution precipitates white sodium hexahydroxoantimonate(V).
Na+ + [Sb(OH)6]- = Na[Sb(OH)6]
Reactions of potassium ion (K+)

For testing the reactions of potassium ion, potassium chloride [KCl] stock
solution is used.

Experiment 4.1.49
In a not too dilute solution sodium hydrogen tartrate precipitates potassium
hydrogen tartrate as white crystals.

29

COO K+ +

COOK

CH OH
CH OH
COOH

CH OH
CH OH
COOH

Experiment 4.1.50
Na3[Co(NO2)6], sodium hexanitritocobaltate(III) solution precipitates yellow
potassium hexanitritocobaltate(III). Note: The reagent solution is dark.
3 K+ + [Co(NO2)6]3- = K3[Co(NO2)6]

Experiment 4.1.51
Flame test: (For the performance see Exp. 4.1.43.) Potassium chloride vapour
colours the flame pale violet. Traces of sodium may obscure the colour, but viewed
through a cobalt glass the yellow colour of sodium can be filtered.

Reactions of ammonium ion (NH4+)

For testing the reactions of ammonium ion, ammonium chloride [NH4Cl]


stock solution is used.

Experiment 4.1.52
On addition of a strong base, e.g. NaOH, ammonia gas evolves. Stick a piece
of wet red litmus paper into the middle of the convex side of a watch glass. In another
watch glass mix 2-2 drops of ammonium chloride and sodium hydroxide solutions
and cover the watch glass with the first one. The blue colour of the litmus paper
indicates the evolution of ammonia gas. (Difference from potassium ion.)
NH4+ + OH- = NH3 + H2O

30

Experiment. 4.1.53
Na3[Co(NO2)6] solution, precipitates yellow ammonium
cobaltate(III).
3 NH4+ + [Co(NO2)6]3- = (NH4)3[Co(NO2)6]

hexanitrito-

Experiment 4.1.54
The most sensitive reaction of ammonium ion is the Nessler reaction. In
strongly basic medium potassium tetraiodomercurate(II), [HgI4]2- produces brown
precipitate or brownish-yellow coloration depending on the concentration of the test
solution. Basic mercury(II) amido iodide forms.
NH4+ + 2 [HgI4]2- + 4 OH- = HgO Hg

31

NH2
I

+ 7 I- + 3 H2O

DETECTION OF ANIONS

Similarly to cations, anions are classified by testing with HNO3, BaCl2 or


Ba(NO3)2 and AgNO3 solutions. It should be noted that while the cations are
separable by means of the group reagents, anions cannot be so.
Group-1 anions react with strong acids to form gases or a precipitate: CO32-,
HCO3-, SO32-,S2O32-, S2-, SiO32-, ClO-.
Group-2 anions do not react with acids but react with BaCl2 or Ba(NO3)2 to
form a precipitate: SO42-, PO43-, BO33-, F-, IO3-, BrO3-.
Group-3 anions give a precipitate with AgNO3: Cl-, I-, Br-, CN-, SCN-,
[Fe(CN)6]4-, [Fe(CN)6]3-.
Group 4 consists of anions having no common reaction. These ions should be
detected individually: NO3-, NO2-, ClO3-, OH-, CH3COO-, (COO)22-.

32

GROUP 1

Reactions of carbonate ion (CO32-)

For testing the reactions of carbonate ion, sodium carbonate [Na2CO3] stock
solution is used.

Experiment 4.1.57 (Group reaction)


Addition of acids causes evolution of carbon dioxide (see also Exp. 4.1.56).
CO32- + 2 H+ = H2O + CO2

Experiment 4.1.58
Barium-nitrate solution precipitates white barium carbonate. The precipitate
dissolves in dilute acids with the evolution of carbon dioxide gas. (Difference from
SO42- and PO43- ions.)
Ba2+ + CO32- = BaCO3
BaCO3 + 2 H+ = Ba2+ + CO2 + H2O

Experiment 4.1.59
The water-soluble carbonates hydrolyze making the solution considerably
basic. The solution dropped with phenolphthalein turns intense pink (difference from
soluble hydrogen carbonates).
CO32- + 2 H2O

2 OH- + H2CO3

33

Reactions of hydrogen carbonate ion (HCO3-)

For testing the reactions of hydrogen carbonate ion, sodium hydrogen


carbonate [NaHCO3] stock solution is used.

Experiment 4.1.60 (Group reaction)


Acids produce evolution of carbon dioxide.
HCO3- + H+ = H2O + CO2

Experiment 4.1.61
Hydrogen carbonate ion is less basic than carbonate ion. Phenolphthalein
shows pale pink colour only.
HCO3- + H2O

OH- + H2CO3

Reactions of hypochlorite ion (ClO-)

For testing the reactions of hypochlorite ion, sodium hypochlorite [NaOCl]


stock solution is used.

Experiment 4.1.62 (Group reaction)


HCl generates Cl2 gas which can be detected by a wet iodo-starch paper held
to the opening of the test tube. Cl2 oxidizes iodide ions to I2, and the latter forms a
blue inclusion complex with starch.
Cl- + ClO- + 2 H+ = H2O + Cl2
2 I- + Cl2 = I2 + 2 Cl-

34

GROUP 2

Reaction of sulphate ion (SO42-)

Sulphuric acid stock solution is used for testing sulphate ions.

Experiment 4.1.63 (Group reaction)


Barium nitrate solution precipitates powdery barium sulphate which is
insoluble in dilute acids (difference from carbonate and phosphate ions).
Ba2+ + SO42- = BaSO4
Reactions of phosphate ion (PO43-)

For tests of phosphate ion, disodium hydrogen phosphate [Na2HPO4] stock


solution is used.

Experiment 4.1.64 (Group reaction)


Ba(NO3)2 solution in neutral or slightly alkaline medium precipitates white
barium hydrogen phosphate which is soluble in dilute acids (difference from sulphate
ion).
HPO42- + Ba2+ = BaHPO4

Experiment 4.1.65
Magnesia mixture in alkaline medium precipitates magnesium ammonium
phosphate as white crystals. The precipitate dissolves in acids (see also Exps. 4.1.46
and 6.10).

PO43- + Mg2+ + NH4+ = MgNH4PO4

35

Experiment 4.1.66
In a solution acidified with HNO3, large excess of ammonium molybdate
precipitates yellow ammonium phosphomolybdate, (NH4)3[P(Mo3O10)4]. To 1-2
drops(!) of phosphate solution, 1 cm3 nitric acid is added, followed by a gradual
addition of ammonium molybdate until a yellow colour develops. In a few minutes,
yellow crystals separate.
4 H2[Mo3O10] + PO43- + 3NH4+

(NH4)3[P(Mo3O10)4] + 4 H2O

GROUP 3

Reactions of chloride ion (Cl -)

For tests of chloride ion, sodium chloride stock solution is used.

Experiment 4.1.67 (Group reaction)


AgNO3 solution precipitates white, curd-like, crystalline silver chloride.
Cl- + Ag+ = AgCl
The precipitate is divided into four test tubes, and the following tests are performed:
a) Adding nitric acid, the precipitate does not dissolve,
b) adding ammonia, the precipitate dissolves forming diamminesilver complex ion,
c) adding sodium thiosulphate, solution the precipitate dissolves in the form of
complex dithiosulphatoargentate ions,
d) allowed to stand, the white precipitate gradually turns grey due to the
photosensitivity of silver salts:
AgCl + 2 NH3 = [Ag(NH3)2]+ + ClAgCl + 2 S2O32- = [Ag(S2O3)]3- + Cl2 AgCl + h = 2 Ag + Cl2

36

Reactions of iodide ion (I -)

For testing iodide ion, potassium iodide stock solution is used.

Experiment 4.1.68 (Group reaction)


AgNO3 precipitates yellow powder of silver iodide.
I- + Ag+ = AgI

The precipitate is divided into four test tubes and the following tests are performed:
a) When adding nitric acid, the precipitate does not dissolve,
b) adding ammonia, the precipitate dissolves partly forming diamminesilver complex
ion,
c) adding sodium thiosulphate solution, the precipitate dissolves easily in the form of
complex dithiosulphatoargentate ions,
d) allowed to stand, the yellow precipitate turns gradually grey due to the
photosensitivity of silver salts:
AgI + 2 NH3 = [Ag(NH3)2]+ + IAgI + 2 S2O32- = [Ag(S2O3)2]3- + I2 AgI + h = 2 Ag + I2

Experiment 4.1.69
Chlorine water sets free elementary iodine from iodides.
2 I- + Cl2 = 2 Cl- + I2
The brown solution is divided into two test tubes and
a) starch solution is added to form a blue inclusion complex. The reaction is extremely
sensitive to iodine.
b) carbon tetrachloride is added and the mixture is shaken. In the water-insoluble,
oxygen-free organic solvent iodine shows violet colour.

37

Experiment 4.1.70
Bromine water acts similarly to chlorine.
2 I- + Br2 = 2 Br- + I2

GROUP 4

Reactions of nitrite ion (NO2-)

For the tests of nitrite ion, sodium nitrite [NaNO2] stock solution is used.

Experiment 4.1.71
A little NaNO2 solution is acidified with acetic acid, and FeSO4 solution is
added. The solution turns brown due to the formation of (unstable) nitroso iron
sulphate, [Fe(NO)SO4]. (Nitrate reacts similarly but only in presence of cc. H2SO4.)

Experiment 4.1.72
To 1-2 cm3 distilled water 1-2 drops of NaNO2 solution are added. Then,
1-1 cm3 of Griess-Ilosvay 1 and 2 reagent solutions in this order. In dilute nitrite
solution intense red colour develops. (At higher concentrations nitrite ion oxidizes the
red dye and the solution turns pale yellow.)
In acidic medium aromatic amines like sulphanilic acid (reagent 1) are
diazotized by nitrous acid and the diazonium salt formed reacts with other aromatics
like -naphthylamine (reagent 2) in an azo-coupling reaction resulting a deeply
coloured dye.

HOS O2

+
NH2 + HNO 2 + H

N N

HOS O2

+
HOSO 2

N N

HOSO 2

NH2

38

N N

+
+ 2 H2O

NH2 + H +

Reactions of nitrate ion (NO3-)

For the tests of nitrate ion, sodium nitrate [NaNO3] stock solution is used.

Experiment 4.1.73
To a little NaNO3 solution cc. H2SO4 is added carefully, the solution is
cooled under the tap and iron(II) sulphate solution is carefully layered on. A brown
ring forms known from the reactions of nitrite ion (see Exp. 4.1.71).

Experiment 4.1.74
On addition of Zn + HCl, nitrate ion can be reduced to nitrite and gives
positive Griess-Ilosvay reaction (see Exp. 4.1.72).
Procedure:
Repeat Exp. 4.1.72 with sodium nitrate solution, adding zinc powder to the
reaction mixture.
NO3- + Zn +H+ = NO2- + Zn2+ +H2O

39

SIMPLE ANALYSIS OF CATIONS AND ANIONS

Experiment 4.1.76
Simple analysis of cations and anions
The simple analysis of cations and anions of medical importance in cases
when only one cation and one anion are present is performed as shown in Tables 1
and 2.
Procedure:
Prior to the systematic analysis it is strongly recommended that preliminary
tests be carried out with a small portion of the sample (colour, odour, crystal form,
etc.). Then, 0.5-1 g of the sample is dissolved in 30-40 cm3 water. One-third of this
stock solution is used to test for cations, another third for anion analysis, the rest is put
aside. It is advisable to check the pH of the stock solution before systematic analysis.
First the cations are identified, since their knowledge limits the number of the
possible counterions. E.g., if the sample is water-soluble and Hg22+ cation has been
found, the presence of Cl- and I- ions should be excluded.
After the identification of the ion according to Tables 1 and 2, all the
characteristic reactions of the suspected ion should be positive to accept the analysis
correct. The analysis process should be described in details in the notebook, including
visual observations and chemical equations.

40

Table 1; Simple analysis of cations


Sample

II

Reagent

Observation

Ion?

X (= stock solution) + HCl:

white precipitate

Pb2+ or Hg22+

X + NaOH:

white precipitate
black precipitate

Pb2+
Hg22+

solution I + H2S:

yellow precipitate *

As3+

X + NH4OH:

III

X + (NH4)2S:

black precipitate

Hg2+ or Cu2+

white precipitate

Hg2+

blue precipitate

Cu2+

white precipitate

Zn2+

green prec., soluble in HCl

Cr3+

black precipitate
greenish precipitate

Fe2+

brown precipitate

Fe3+

blue precipitate

Co2+

X + Na2CO3:

white precipitate

Ca2+ or Mg2+

X: flame test:

brick-red

Ca2+

negative

Mg2+

yellow

Na+

pale violet

K+

X + NaOH:

IV

Fe2+, Fe3+or Co2+

If all reactions have been


negative so far:
X: flame test:

X + Nessler's reagent:

brown precipitate

X + acid-base indicator:

acidic

NH4+
H+

* In presence of oxidative ions (Fe3+or NO2-), milky colloidal solution of sulphur may form.

41

Table 2; Simple analysis of anions


Sample

Reagent

+ HCl

Observation

Ion?

CO32-, HCO3-

gas evolution

or ClO-

the gas

CO2:

CO32- or HCO3ClO-

Cl2 (KI paper):

+ Ba(NO3)2

white precipitate:

(CO32-) *,
SO 2- or PO 34

a) prec. + HNO3

+ HNO3 + AgNO3

dissolves:

(CO32-) *
PO 3-

insoluble:

SO42-

precipitate:

Cl- or I-

dissolves with effervescence:

a) prec. + NH4OH

soluble in a) and b):

b) prec.+Na2S2O3

soluble in b) only:

+ Griess-Ilosvay reagent

ClI-

red colour:

NO2-

red colour:

NO3-

if negative for NO2addition of Zn + HCl

* If detection failed in Group 1 (solution too dilute).

42

4.1 QUALITATIVE CHEMICAL ANALYSIS

SELF-TEST QUESTIONS

1.

Why can the sulphides of the cations of the first two analytical groups be
precipitated with H2S in acidic medium?

2.

Explain, why it is unsuccessful in the case of Group-3 cations and succeeds


when applying (NH4)2S.

3.

What do you know about the temperature dependence of the solubility of


lead(II) chloride?

4.

Explain the dissolution of lead(II) hydroxide in excess NaOH solution?

5.

How can you distinguish between Hg2+ and Pb2+ ions?

6.

Write equation for dissolution of copper(II) hydroxide precipitate in excess


ammonia solution.

7.

Write equations for the reactions of potassium iodide with Hg2+, Pb2+ and
Cu2+ ions.

8.

What is the common reagent of the fourth analytical group of cations?

10.

How can Hg22+, Hg2+, Pb2+, Cu2+, Fe2+, Fe3+, Mg2+ and NH4+ ions be
distinguished using a single reagent?

11.

Propose a further reagent to distinguish Hg22+ and Hg2+ ions.

12.

How could you prepare Nessler's reagent and which ion is detected with it?

13.

Describe the essence of the Bettendorf-reaction.

14.

Write down the reactions suitable to distinguish Fe2+ and Fe3+ ions.

15.

During storage, iron(II) ions are easily oxidized to iron(III) ions by the
atmospheric oxygen. Propose a reaction to check the purity of an iron sulphate
sample.

16.

What is the most sensitive reaction of Ca2+ ions?

17.

Why is it impossible to precipitate Mg(OH)2 in the presence of ammonium


ions?

18.

How can Ca2+ and Mg2+ ions be distinguished?

19.

How can Na+ and K+ ions be distinguished?

20.

How can K+ and NH4+ ions be distinguished?

21.

Collect methods for detection of H+.

43

4.1 QUALITATIVE CHEMICAL ANALYSIS

22.

What are the common reagents for the Group 1, 2 and 3 anions?

23.

How can you detect and explain the basicity of CO32- and HCO3- solutions?

24.

How could you detect OCl- ion?

25.

How could you detect and distinguish SO42- and PO43- ions?

26.

How to distinguish Cl- and I- ions?

27.

How to distinguish NO2- and NO3- ions? Describe the Griess-Ilosvay


reaction (see Organic Chemistry).

44

45

9. APPENDIX

9.1. INORGANIC CHEMISTRY


A short overview
INTRODUCTION

The aim of this compilation is to offer the students a supplement


a./ for recapitulation their recent knowledge having been acquired at the high school,
b./ for internalization additional practically interesting pieces of information about elements and
compouns, exceeding the limited subject of the laboratory practices and
c./ of short references to the biomedical importance of some inorganic substances.
It should be noted that this short overview comprises only supplementary material;
theoretical and analytical details can be found elsewhere!
Inorganic chemistry studies the structures and structure-property relationships of the
elements and their compounds except those containing carbon-hydrogen bonds. (The latters are
studied by Organic Chemistry). Considering that the chemical-physical properties of the elements
are mostly determined by their electronic structure (in close connection with their position in the
periodic table), it is plausible to discuss them according to the periodic law:
1./ Alkali metals and alkali earth metals (elements of the s-block except H and He);
2./ Main group metals (Sn, Pb, Bi);
3./ Transition metals (elements of the d-block);
4./ Metalloids (the lower left area of the p-block);
5./ Non-metals (elements of the p-block with high electronegativity values):
6./ Noble gases (the elements of the column VIII. of the periodic law).

46
CLASSIFICATION OF THE INORGANIC COMPOUNDS
The scientific classification of the inorganic compounds is based on their bonding systems
and crystal types: Ionic compounds usually form ionic crystals; covalent compounds are of
network or molecular crystals; the so-called intermetallic compounds exist in the form of a
metallic crystal lattice. This grouping allows a rather easy understanding of structure-property
relationships but exceeds our requirements. Considering that most of the inorganic compounds
are either hydrogen and/or oxygen compounds or salts, the following classification may be
useful:
Hydrogen compounds
Hydrogen forms so-called binary hydrides with almost all elements.
Ionic hydrides are formed with the elements of the lowest electronegativity values (sblock elements) in which hydride anion (H-) exists (NaH, CaH2). These salt-like hydrides are
strong bases (proton acceptors, electron pair donors) and strong reducing agents (electron
donors).
The hydrides of the non-metallic elements (p-block elements) are covalent compounds
(volatile, of molecular crystal lattice). Their properties depend strongly on the partner atoms.
Thus, the hydrogen halides are polar, soluble in water, their solutions are acidic and their acid
strength increases with the atomic number of the halogen. Hydrides of the oxygen group elements
are slightly acidic (H2S), H2O is amphoteric. The elements of the nitrogen group form basic
hydrides (NH3, PH3), the carbon group hydrides are neutral. The hydrides of silicon, aluminium
and boron represent a transition between the covalent and salt-like ones.
Hydrides of the d-block elements (transition metals) are of metallic type in which
hydrogen atoms(!) occupy the space between the metal ions in the crystal lattice.
Oxygen compounds
The oxygen compounds are classified as oxides, hydroxides and oxoacids. Salts of
oxoacids will be discussed separately.
Oxides
a./ Basic oxides are the oxides of the elements of lowest electronegativity, reacting with
water to form the corresponding hydroxide bases, i.e. they are base anhydrides. Examples: The

47
oxides of the s-block elements (Na2O, K2O, CaO, BaO), a few of the p-block elements (Bi2O3)
and of the transition metals of lower oxidation state (FeO, MnO, CoO).
b./ Acidic oxides: To this group belong the oxides of the highly electronegative nonmetals and metalloids (SO2, SO3, P2O3, P2O5, As2O3, As2O5, CO2, SiO2, NO2, N2O3, N2O5,
etc.) and a few of the transition metals at higher oxidation state (CrO3, Mn2O7, V2O5, OsO4).
These oxides are acid anhydrides; They hydrolyze with water to form acids.
c./ Neutral oxides: This group comprises first of all H2O (amphoteric), NO, CO, N2O
(not being anhydrides) and the water-insoluble oxides ( Al2O3, Fe2O3).
Hydroxides and oxoacids
The basic oxides react with water to form bases, the acidic oxides to form oxoacids. In
aqueous solution, bases dissociate into hydroxide ion and a metal ion, the acids into hydrogen
(oxonium) ion and an oxo-anion. Acids and bases react to form water and a salt. The basic
strength of hydroxides increases with the atomic radius of the metal atom, the acid strength
increases with the oxidation number of the central atom. There is an intermediate group of
hydroxides (amphoteric hydroxides) exhibiting both weakly acidic and basic reactions depending
on the medium.
Acid-base character of X(OH)n compounds

Oxidation
number of X

General
formula

Basic

Amphoteric

Acidic

+1

XOH

Li, Na, K,

Cl

+2

X(OH)2

Mg, Ca, Ba, Cr, Mn,


Fe, Co, Ni, Cu

Be, Zn, Sn, Pb

+3

X(OH)3

Fe, Bi

Al, Cr, As, Sb

B, P

+4

X(OH)4

Pb, Sn

C, Si, S, Se

As

P, N, Cl, Br, I

H2XO3
+5

H3XO4
HXO3

48

+6

H2XO4

S, Se, Mo, Cr, Mn

+7

HXO4

Mn, Cl, I

A few examples:
Hydrolysis of a basic oxide:

CaO + H2O

= Ca(OH)2

Dissociation of the base:

Ca(OH)2

Ca2+

Hydrolysis of an acidic oxide:

CO2

H2O

2 OH=

H2CO3

Certain acidic oxides, depending on the stoichiometric ratio of added water, form different acids:
Adding maximum amount of water orthoacids, with less amounts pyro- and metaacids are
produced respectively, e.g.:
P2O5

3 H2O

2 H3PO4

orthophosphoric acid

P2O5

2 H2O

H4P2O7

pyrophosphoric acid

P2O5

H2O

metaphosphoric acid

2 HPO3

There are acid anhydrides which disproportionate during hydrolysis. These are regarded as the
common anhydrides of two different acids, e.g.:

2 NO2

H2O

HNO3

Dissociation of an acid:

H2CO3

Reaction of an acid and a base:

Ca(OH)2

+
=

HNO2
2 H+

CO32-

+ H2CO3 = CaCO3 + 2 H2O

Basic oxides react with acids, acidic oxides with bases and basic oxides with acidic oxides,
respectively, also to form salts.:
Basic oxide with an acid:

CaO + H2CO3

Acidic oxide with a base:

CO2

Basic oxide with acidic oxide:

= CaCO3

Ca(OH)2

CaO + CO2

+ H2O

= CaCO3
=

CaCO3

+ H2O

49

Salts
Salts are regarded as products of the acid-base (neutralization) reactions (i.e. they are not
oxygen containing compounds by all means. See, e.g. NH3 + HCl = NH4Cl). Salts can be
classified as follows:
a./ Normal salts: Salts resulted in a stoichiometric neutralization reaction:
2 NaOH

H2SO4

Na2SO4

2 H2O

3 KOH

H3PO4

K3PO4

3 H2O

b./ Acid salts: Salts formed by an incomplete neutralization of a polybasic acid. The
name: acid salt refers to the composition, not to their hydrolysis! (Their reactions in aqueous
solution are not acidic by all means!):
KOH

H3PO4

KH2PO4

H2O

2 KOH

H3PO4

K2HPO4

2 H2O

NaOH

H2CO3

NaHCO3

H2O

KOH

H2SO3

KHSO3

H2O

c./ Base salts are products of a partial neutralization of a polyvalent (polyacidic) base.
The name: base salt refers to the composition, not to their hydrolysis! (Their aqueous solutions
are not basic by all means!):
Bi(OH)3

HNO3

Bi(OH)2NO3

Sb(OH)3

HCl

SbOCl

H2O

+ 2 H2O

d./ Mixed salts: Salts formed in a reaction of one base with two acids:
Ca(OH)2

Cl2

CaClOCl

H2O

50
e./ Double salts: Occasionally, from a solution of two different salts, uniform crystals are
obtained. The composition of these crystals is stoichiometric, according to the sum of the two
formulas and, when dissolved, dissociate into all ionic components:
K2SO4

Al2(SO4)3

2 KAl(SO4)2

(alum)

When dissolved in water:

or, e.g .

KAl(SO4)2

(NH4)2SO4

+FeSO4

K+

Al3+

2 SO42-

(NH4)2Fe(SO4)2 (Mohr's salt)

When dissolved in water:


(NH4)2Fe(SO4)2

2 NH4+

Fe2+

+ 2 SO42-

f./ Complex salts are coordination compounds composed of an undissociable, so-called


complex ion and a dissociable counterion. The complex ion itself is composed of a central metal
ion surrounded by the so-called ligands, coordinatively bound to the central ion. The number of
the ligands is called coordination number.
AgCl + 2 NH3

[Ag(NH3)2]Cl

When dissolved:
[Ag(NH3)2]Cl = [Ag(NH3)2]+ + Cl-

(diamminesilver(I) chloride

Sodium dithiosulphatoargentate(I) behaves similarly in aqeous solution:


Na3[Ag(S2O3)2]

= 3 Na+

[Ag(S2O3)2]3-

Thio compounds
In both inorganic and organic chemistry, compounds having divalent sulphur atom(s)
instead of oxygen atom(s) of a structurally analogous, known compound, are called thio
compounds. Thus, the thio analogue of water is hydrogen sulphide (H2S), those of oxides are the
sulphides (CO2 / CS2, CaO / CaS etc.), that of sulphuric acid is thiosulphuric acid (H2SO4 /

51
H2S2O3), that of arsenous acid is thioarsenous acid (H3AsO3 / H3AsS3), that of cyanic acid is
thiocyanic acid (rodanic acid) (HOCN / HSCN), etc..

Acyl groups
Acyl groups, as imaginary derivatives of oxoacids, can be obtained by the removal of the
hydroxyl groups (not hydroxide ions!) from the acid molecules. Thus, acyl groups have free
valence (-ies) useful to construct formulas of acid derivatives, e.g. acyl halides:
A few examples:
Oxoacid

Acyl group

Acyl chlorlide

nitrous acid: HNO2 nitrosyl group NO

nitrosyl chloride

ClNO

nitric acid:

NO2

nitryl chloride

ClNO2

=SO

sulphinyl chloride

Cl2SO

HNO3 nitryl group

sulphurous a.: H2SO3 sulphinyl

or thionyl group

or thionyl chloride

sulphuric a.: H2SO4 sulphonyl


=SO2
or sulphuryl group

sulphonyl chloride

carbonic a.: H2CO3 carbonyl g.

carbonyl chloride

Cl2SO2

or sulphuryl chloride

=CO

COCl2

or phosgene
phosphoric a.: H3PO4

phosphoryl g.

PO

phosphoryl chloride
or phosphorus oxychloride

POCl3

52

THE NOMENCLATURE OF INORGANIC IONIC COMPOUNDS

Compounds can be described by their formulas and by their systematic, trivial or


pharmaceutical (Latin) names. In both formulas and names cation(s) precede(s) anion(s), e.g.
NaCl: sodium chloride; K2HPO4: dipotassium hydrogen phosphate.
If the cation may exist in different oxidation states, the oxidation number of it is given in
Roman numerals in brackets attached to the name of the cation, like Hg2Cl2: mercury(I) chloride
and HgCl2: mercury(II) chloride.
Anions of non-oxoacids have a name ending -ide, in Latin -atum, e.g.. Br-: bromide /
bromatum; CN: cyanide / cyanatum; etc. Names of the anions of oxoacids usually end -ate / icum, e.g. CO32: carbonate / carbonicum. If the central atom of the anion can exist in two
oxidation
states
the
name
of
the
most
oxidized
anion
ends
2
2
-ate / -icum, the other ends -ite / -osum, e.g. SO4 : sulphate / sulfuricum, but SO3 : sulphite /
sulfurosum. In case of four different oxidation states the lowest oxidation state is referred by
hypo- / hypo- the highest one by per- / hyper- prefixes. (see the oxoacids of chlorine in Table 1.).
The formulas of the complex ions or neutral complexes are put in square brackets, those
of the ligands in brackets. Inside the formula of a complex ion, the atomic symbol of the central
atom or ion precedes the formula(s) of the ligands, e.g. [Pt(Cl)6]2, [Ni(CO)4]. The names of the
ligands end -o except H2O: aqua, NH3: ammine and CO: carbonyl. The names of the central
atoms of the neutral complex molecules and cations are the usual ones, the names of the complex
anions end -ate. The oxidation state of the metal is put in brackets after the name, e.g. [Fe(CO)5]:
hexaaquairon(II) ion,
but
[Fe(CN)6]4:
pentacarbonyliron(0)
and
[Fe(H2O)6]2+:
hexacyanoferrate(II) ion.

53
Table 1. Examples of naming inorganic compounds

F
Cl
Br

Formula

Name

Latin name

Anions

( trivial name )
...........................ide

.....................atum

fluoride
chloride
bromide

fluoratum
chloratum
bromatum

iodide

iodatum

CN
OH

cyanide
hydroxide

cyanatum
hydroxydatum

O 2
S 2

oxide
sulphide

oxydatum
sulfuratum

hydride

hypo...........ite
hypochlorite
...................ite

hypo..................osum
hypochlorosum
....................osum

ClO2
NO2

chlorite
nitrite

chlorosum
nitrosum

SO32

sulphite

sulfurosum

arsenite
.......................ate

arsenicosum
............................icum

ClO3
BrO3

chlorate
bromate

chloricum
bromicum

IO3
NO3

iodate
nitrate

iodicum
nitricum

CO32
SO42

carbonate
sulphate

carbonicum
sulfuricum

S2O32

thiosulphate

thiosulfuricum

PO4
AsO43

phosphate
arsenate

phosphoricum
arsenicum

MnO42
OCN
SCN

manganate
cyanate
thiocyanate (rodanide)

manganicum
cyanicum
thiocyanicum

OCl

AsO3

per...............ate
MnO4
ClO4

permanganate
perchlorate

hyper................icum
hypermanganicum
hyperchloricum

54
Acids
HCl

Name
hydrogen chloride

Latin name
acidum chloratum

HI
HCN

hydrogen iodide
hydrogen cyanide

H 2S
HOCl
HClO2

hydrogen sulphide
hypochlorous acid
chlorous acid

ac. hypochlorosum
ac. chlorosum

HClO3

chloric acid

ac. chloricum

HClO4
HNO2

perchloric acid
nitrous acid

ac. hyperchloricum
ac. nitrosum

HNO3
H2SO3

nitric acid
sulphurous acid

ac. nitricum
ac. sulfurosum

H2SO4

sulphuric acid

ac. sulfuricum

H3PO3
H3PO4
H2CO3

orthophosphorous acid
orthophosphoric acid
carbonic acid

ac. phosphorosum
ac. phosphoricum
ac. carbonicum

H2SiO3

silicic acid

ac. silicicum

KOH

potassium hydroxyde

kalium hydroxydatum

Ca(OH)2
Fe(OH)2

calcium hydroxyde
iron(II) hydroxyde

calcium hydroxydatum

Fe(OH)3

iron(III) hydroxyde

Bases

Salts
NaCl

sodium chloride (table

natrium chloratum !!!

salt)
NaClO3
As2S3

sodium chlorate
arsenic(III) sulphide

As2S5

arsenic(V) sulphide

CaSO4

calcium sulphate

natrium chloricum !!!

calcium sulfuricum

(gypsum)
MgSO4
Na2SO4

magnesium sulphate
(bitter salt)
sodium sulphate

magnesium sulfuricum
natrium sulfuricum

(Glauber's salt)
CuSO4
FeSO4

copper(II) sulphate
iron(II) sulphate

cuprum sulfuricum
ferrosum sulfuricum

55
Fe2(SO4)3
Hg2Cl2
HgCl2

iron(III) sulphate
mercury(I)chloride

hydrargyrum chloratum

(calomel)

mite

mercury(II)chloride
(sublimate)

Formula
NaH2PO4

Name
sodium dihydrogen

Latin name

phosphate
Na2HPO4

disodium hydrogen
phosphate

Na3PO4
Bi(OH)2NO3

trisodium phosphate
bismuth dihydroxide

bismuthum subnitricum

nitrate
(basic bismuth nitrate)
Complexes
[Fe(CO)5]

pentacarbonyliron(0)

[Ag(NH3)2]Cl

diamminesilver(I)
chloride

Na3[Ag(S2O3)2]

sodium
dithiosulphatoargentate(I)

K4[Fe(CN)6]

potassium
hexacyanoferrate(II)

K3[Fe(CN)6]

potassium
hexacyanoferrate(III)

K2[HgI4]

potassium
tetraiodomercurate(II)

Fe3[Fe(CN)6]2

iron(II)
hexacyanoferrate(III)

Fe4[Fe(CN)6]3

iron(III)
hexacyanoferrate(II)

For the practice, one of the most important properties of compounds is their solubility.
The water-solubility of the most common inorganic salts is tabulated below.

56

Anion

Solubility
Soluble in water

NO3
Cl

every nitrate is soluble


most of chlorides are soluble except: AgCl, Hg2Cl2, PbCl2

Br

most of bromides are soluble except: AgBr, Hg2Br2, HgBr2 and PbBr2
most of iodides are soluble except: AgI, Hg2I2, HgI2 and PbI2

I
SO42-

most of sulphates are soluble except: CaSO4, SrSO4, BaSO4, PbSO4,


Hg2SO4, Ag2SO4

ClO3
C2H3O2

every chlorate is soluble

every acetate is soluble


Insoluble in water

S2

most of sulphides are insoluble except alkali-, alkali earth metal and ammoniumsulphides

OH

most of hydroxides are insoluble except: alkali hydroxides and Ba(OH)2, Sr(OH)2,
Ca(OH)2

CO3

SO3
PO43

most of carbonates are insoluble except: alkali metal and ammonium carbonates
most of sulphites are insoluble except: alkali metal and ammonium sulphites
most of phosphates are insoluble except alkali metal and ammonium phosphates.

57

9.3 CONCENTRATIONS OF REAGENT SOLUTIONS

Concentrations of reagent solutions made by the technicians in the stock laboratory and not
indicated in the text can be seen below.
Acetic acid
Alcoholic -naphthol
Alum
Ammonia
Ammonia-ammonium-chloride
buffer
Ammonium acetate
Ammonium carbonate
Ammonium chloride
Ammonium iron(III) sulphate
Ammonium molybdate
Ammonium oxalate
Ammonium sulphide
Ammonium thiocyanate
Arsenic trioxide
Barium chloride
Barium nitrate
Benzoic acid
Bettendorf's reagent
Bismuth chloride
Bromine in carbon tetrachloride
Bromine-water
Calcium chloride
Calcium hydroxide
Chlorine-water
Chromium(III) sulphate
Cobalt(II) nitrate
Copper(II) sulphate
Dimethyl glyoxime
2,4-Dinitrophenyl hydrazine HCl
3,5-Dinitrobenzoic acid
Disodium hydrogen phosphate
Eriochrome black T
Ethanolic silver nitrate

12 %
5%
5%
5%
0,8 % ammonium-chloride + 0,33 % ammonia
8%
10 %
10 %
5%
5 %, in 4 % ammonia solution
3%
5 % ammonia solution saturated with H2S gas
0,90 %
0.5 % (dissolves in hot water!)
5%
9%
0,12 %
10 % tin(II) chlorde in cc. HCl
4 % + cc. HCl until dissolves
5%
1%
11 %
5%
distilled water saturated with chlorine gas
6%
10 %
4%
1 % in ethanol
2 %, in 40 % ethanol
0,21 %
7%
1 %, in 70 % isopropanol
2%

58
Fehling I
Fehling II
Formaldehyde
Fructose
Glucose
Glycine
Glycogen
Griess-Ilosvay I
Griess-Ilosvay II
Hydrochloric acid
Hydroquinone
Iodine
Iron(II) sulphate
Iron(III) chloride
Lactose
Lead(II) acetate
Lead(II) nitrate
Lecithin
Magnesia mixture
Magnesium chloride
Magnesium sulphate
Mercury(I) nitrate
Mercury(II) chloride
Methanolic -naphthol
Methyl orange
Methyl red
Methylamine HCl
-Naphthol
Nessler-reagent
Nickel sulphate
Ninhydrin
Nitric acid
ortho-Toluidine
Phenol
Phenolphtalein
Phenylhydrazine HCl
Picric acid
Potassium chloride
Potassium chromate
Potassium chromate (acidic)

4 % copper(II) sulphate
20 % K-Na-tartarate in 15 % NaOH solution
38 %
5%
10 %
1%
1%
1 % sulphanilic acid in 40 % acetic acid
3 % -naphthylamine in 30 % acetic acid
5%
5%
1 % +2 % KI
10 %
8%
5%
10 %
8%
0,2 %
10 %; see also Exp. 6.10!
10 %
5%
3 %, + nitric acid until dissolves
1,5 %
1%
0,10 %
0,2 %, in 60 % ethanol
40 %, acidified with a little HCl
5%
6 % Hg(II) chloride + 7,5 % KI in 20 % NaOH
5%
0,2 % in ethanol
20 %
6 % + 0,15 % thiocarbamide in cc. acetic acid
5%
1 % in 70 % ethanol
10 %
5%
8%
3%
3 %, in 20 % sulphuric acid

59
Potassium chromium(III) sulphate
Potassium hexacyanoferrate(II)
Potassium hexacyanoferrate(III)
Potassium
hexahydroxoantimonate(V)
Potassium iodide
Potassium permanganate
Protein
Rubeanic acid
Saccharose
Salicylic acid
Silver nitrate
Sodium acetate
Sodium acetate, concentrated
Sodium carbonate
Sodium chloride
Sodium dihydrogen phosphate
Sodium hexanitritocobaltate(III)
Sodium hydrogen carbonate
Sodium hydrogen tartarate
Sodium hydroxide
Sodium hypochlorite
Sodium nitrate
Sodium nitrite
Sodium nitroprusside
Sodium thiosulphate
Starch
Sulphosalicylic acid
Sulphuric acid
Thymol blue
Thymolphthalein
Trichloroacetic acid
Trisodium phosphate
Tryptophane
Zinc sulphate

5%
2%
2%
2%
2%
0,3 % in 5 % sulphuric acid
4-5 egg-whites in 1 dm3 water
0,1 %, in 65 % ethanol
20 %
1%
0.8 %
11 %
32 %
5%
8%
5%
40 %, in 3 % acetic acid
9%
8%
5%
2%
5%
5%
1 %; unstable!
10 %
1 %-os, + 0,1 % salicylic acid
20 %
10 %
0,5 % in ethanol
0,1 %, in 50 % ethanol
0,16 %
5%
0,5 %
4%

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