Practical General and Physical

Chemistry

El-Zeiny Mousa Ebeid

Professor of Physical Chemistry

2024
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Student Name: …………………………………………………

Student ID: …………………….

College: ………………………………….

Group/Section: ……………………………..

Academic Year/Semester: ……………………………..

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 Contents

1 Ionic equilibrium 1
2 A redox reaction caused by light 4
3 Preparation of gold nanoparticles AuNPs using sunlight. 6
4 Corrosion of iron 9
5 Synthesis of iron oxide nanoparticles 12
6 Thermochemistry 20
7 Laser and X-Ray diffraction 23
8 Atomic weight of a metal by gas evolution 27
9 Study of heating and cooling curves; changes of state. 31
10 Miscibility as a function of temperature 38
11 Volume changes upon mixing 46
12 The salting out of ethanol and water 47
13 The catalytic decomposition of hydrogen peroxide 48
14 Kinetics of the reaction between iodide and hydrogen 55
peroxide in an acidic medium
15 Molecular weight of a polymer from viscosity measurements 58
16 Solubility of oxalic acid as a function of temperature 64
17 Diffusion of ammonia and hydrogen chloride gas-verification 68
of Graham’s law of diffusion
18 The Density of a Single Crystal of Ammonium Oxalate 71
Monohydrate by the Floatation Method
19 Chemical synthesis gold nanoparticles 73

e
Preface
The aim of this book is to cover practical laboratory work for
freshman general and physical chemistry university course. It gives the
freshman student fundamentals of collecting data and analyzing these
data. It also gives a reasonable background in laboratory safety that would
enable the in- experienced worker to avoid laboratory accidents.
I tried to include experiments giving as wide an experience as
possible avoiding the use of expensive equipment. This was done without
affecting the merit of scientific outcome, gained skills and philosophy
involved in general chemistry. Many of the experiments were adapted
from leading international journals including the Journal of Chemical
Education, The Chemical Educator and Chemistry in Britain. Many of the
listed experiments thoroughly test and demonstrate the principles
discussed in lectures of the general and physical chemistry course. It is
possible to synchronize the laboratory work with lectures. Each
experiment is preceded by an outline of the basic theory and principles
upon which it is based in order to link the laboratory work even more
closely to the lectures. Added questions at the end of experiments are
designed to encourage students to think. The arrangement of
experiments in this section is according to subjects and it will be noticed
that more experiments than can be performed during a regular 14 weeks
semester are introduced for better selection.
At the end of the book, appendix is mentioned giving important
physical constants, this data is certainly of great help to students,
instructors and laboratory technicians.

El-Zeiny M. Ebeid
Professor of Physical Chemistry

f
g
Experiment 1: Ionic Equilibrium.

Objective:
To study different equilibrium systems including common ion
effect, exothermic and endothermic processes.
Le Chatelier's Principle states that if a system is at equilibrium and
something is changed so that it is no longer at equilibrium, the system will
respond to counteract that change. If more reactant is added, the
equilibrium will shift forward to consume some of the extra reactant
(since there are more ions available for reaction), resulting in more
product. If some of the product is removed from the system, the
equilibrium will shift forward to produce more of that product. The
equilibrium can be shifted reverse by either adding product to or
removing reactant from the system.

Discussion:
(i) Consider the following equilibrium
+
MX(s) M(aq) + X-(aq)
where (aq.) stands for aqueous or solvated ions. If we add either X- or M+
from an external source, this will shift the equilibrium towards the
formation of the solid. A simple demonstration can be carried out as
follows:
Prepare a clear saturated solution of sodium chloride. Transfer
about 3 ml of this solution to a dry clean test tube. Add a few drops of
concentrated HCl from a plastic dropper and notice the precipitation of
white NaCl crystals in the test tube.
+
NaCl(s) Na(aq) + Cl-(aq)
→ H+(aq) + Cl-(aq)
HCl ⎯⎯
Cl-(aq) is the common ion between NaCl and HCl that shifts the equilibrium
towards the formation of solid NaCl.

(ii) Consider the equilibrium in the cobalt complexes system:

Heat + Co (H2O)26+ + 4Cl- Endothermic
Exothermic
CoCl24- + 6H2O
Dissolve about 0.1 g of cobalt chloride in about 5 ml methanol. Notice the
deep blue color of the solution due to the formation of CoCl24− tetrahedral
cobalt tetrachloride complex. Add water very carefully to the solution in

1
a dropwise addition and notice the change of color to the pink color due
to the formation of the hexa-aquo octahedral complex Co (H2O)26+ .
Immerse the tube in hot water and notice the back change of color back
to the deep blue color since heating shifts the equilibrium towards the
endothermic pathway i.e., towards the formation of CoCl24− . Cool the
contents again in a beaker containing cold water and notice the
appearance of pink color due to the shift of equilibrium towards the
exothermic pathway upon cooling.

(iii) Equilibrium in copper (II) sulphate(*) :

In principle, all chemical reactions are reversible. Moreover, if a
reaction proceeding in one direction is endothermic, then the reverse
reaction is exothermic, and vice versa. The following equation outlines the
chemical changes in this demonstration:
Heat + CuSO4 .5H2O Endothermic
Exothermic
CuSO4 + 5H2O
Blue White
Put one to two grams of copper (II) sulfate pentahydrate,
CuSO4 .5H2O , (of blue color) in a test tube. The crystals may be spread on
the side of the tube for faster dehydration. Then gently heat the tube, in
a horizontal position, over a low gas flame. Continue heating until the blue
crystals change their color to white because of endothermic dehydration
since chemical bonds are present between water and salt in the crystals,
and that the heat is needed to break those bonds. Copper sulphate
without water is white, in contrast to the blue hydrated form. Students
should observe the condensation of the water, separated from the salt,
at the mouth of the tube. Eventually, the heat will evaporate this
condensed water also.
After the complete dehydration, cool the test tube to room
temperature (about 10 minutes). Touch the tube to confirm that it is cool.
Then gradually add drops of water to the tube until the copper (II)
sulphate is completely hydrated and recovers its blue color. This process
is highly exothermic, and the temperature increase can again be tested by
touch. Two cautions (i) students should touch the tube lightly as it may
become quite hot; and (ii) adding excessive water (several milliliters) may
cool the contents of the tube so the temperature rise is not detectable by
touch.
In this demonstration, the reversible reactions of dehydration and
hydration are made visible by the obvious color changes. At the same

(*) C. M. Brozek, J. Chem. Edu., 73 (1996) 837

2
time, the consumption of heat in the forward reaction and heat
production in the reverse reaction is easily tested.

The chromate (K2CrO4) - dichromate (K2CrO7) equilibrium:

2CrO24− + 2H+ H2O + Cr2O27−

Yellow chromate ion and orange dichromate ion are in equilibrium

with each other in aqueous solution. The more acidic the solution, the
more the equilibrium is shifted to favour the dichromate ion. As nitric acid
is added to the potassium chromate solution, the yellow colour turns to
orange. When sodium hydroxide is added to the potassium chromate
solution, the orange colour turns back to yellow. The sodium hydroxide
reacts with hydrogen ions, removing them from the solution. When one
reactant is removed from an equilibrium system, the equilibrium shifts
reverse, in this case forming the yellow chromate ion again.
A 0.1 M potassium chromate, K2CrO4, and a 0.1 M potassium dichromate,
K2Cr2O7, solution will serve as sources for the ions, CrO42- (aq) and Cr2O72-
(aq). Record the colour of each solution.

Place about 1 ml of each solution (K2CrO4 and K2Cr2O7) into 2 separate test
tubes. Add 1 M hydrochloric acid, HCl, drop by drop to each solution.
Record the colour changes observed.

Barium dichromate (orange colour) is soluble in water, but barium

chromate (yellow colour) is insoluble in water. To reacts with chromate
ions (but not dichromate ions) to form an insoluble salt. Yellow barium
chromate precipitate can be converted to soluble orange barium
dichromate by adding a source of H+ ions to the solution.
Place about 1 ml of 0.1 M K2CrO4 in a clean test tube. Add 10 drops of 0.1
M Ba(NO3)2 and notice the formation of a canary yellow precipitate of
BaCrO4. To this precipitate add few drops of 1 M HCl and notice the
dissolution of the yellow precipitate giving orange solution of barium
dichromate.

3
Experiment 2: Redox reactions caused by light.

Objective:
i- To demonstrate that light photons have energy that can cause
chemical reactions.
ii- To deal with the mole concept.
iii- To deal with the oxidation- reduction (redox) concept.
iv- To deal with the concept of spectator ions.

Discussion:
A simple redox reaction that is caused by the reaction between
ammonium oxalate; (NH4 )2 C2O4 and mercuric chloride; HgCl2
(NH4 )2 C2O4 + HgCl2 ⎯⎯ hυ→ Hg Cl + 2CO + 2NH Cl
2 2 2 4
The resulting mercury (I) chloride photoproduct is insoluble in
water and is precipitated as a white precipitate.
The same reaction can be carried out by using K2C2O4, for example,
instead of ammonium oxalate. Hence, both the ammonium and
potassium ions are termed spectator ions in this redox reaction simply
because, unlike the oxalate and mercuric ions, they are not involved in the
redox process.
This reaction is also a reduction-oxidation (redox) reaction in which
the oxalate ion is oxidized to carbon dioxide by losing two electrons. These
two electrons then reduce the mercury (II) ion (Hg2+) to mercury (I)
( Hg22+ ).

Chemicals:
Saturated aqueous solutions of ammonium oxalate and mercuric
chloride

Experimental:
1- In a clean test tube mix about 2 ml of the oxalate solution with 2 ml
of mercuric chloride solution.
2- Divide the mixture into two parts using another clean test tube.
3- Keep one part in a dark place in the laboratory and subject the other
part to direct sunlight for about 10 minutes. Notice the appearance
of a white precipitate of Hg2Cl2 in the irradiated test tube.

4
Calculation of the number of photons
Assuming an efficiency of the photochemical reaction of unity (i.e.
one Hg2Cl2 molecule is produced by every incident photon) one can
roughly estimate the number of incident photons by calculating the
number of formed Hg2Cl2 molecules. This method of calculating the light
intensity by applying chemical reactions is known as “chemical
actinometry”. For a given weight of Hg2Cl2 , the number of molecules is
calculated as follows:
weight weight
Number of moles of Hg2Cl2 = =
molecular weight 472.1
Number of molecules = Avogadro's number × number of moles
= 6.02 × 1023 × number of moles
Calculations:
Weight of Hg2Cl2 = ………………………….. g
Number of moles of Hg2Cl2 = ………………………………………..
Number of Hg2Cl2 molecules = number of photons = …………………

Questions:

 In the reduction-oxidation (redox) reaction

2+ 2- hυ
2Hg + C2O4 ⎯⎯ → Hg22+ + 2CO2
Given that oxidation is the loss of electrons and reduction is the gain of
electrons, then:
- The reactant undergoing oxidation is ……………………………….
- The reactant undergoing reduction is ……………………………….

 Given the above reactants are colorless, then they absorb in the
(UV/ visible) region of light.

 The number of electrons transferred in the above reaction are (1 / 2 /

4) electrons.

5
Experiment 3: Preparation of gold nanoparticles (AuNPs) using sunlight
and ammonium oxalate as a reducing agent.

Nanomaterials are tiny features of nanometer dimensions. To

appreciate this dimension scale, we mention that water molecules are
about
1 nm in size and- an ATP (adenosine triphosphate) biochemical motor
encountered in living cells is about 10 nm in diameter.
Living systems work at the nanoscale level and are governed by
molecular processes. Nanomaterials include diverse features including
semiconductor nanoparticles (also known as quantum dots; CDs), metallic
nanospheres (also known as nanoparticles), metallic nanorods, coated
nanocrystals in the form of nanoshells and core-shell systems. Magnetic
nanoparticles are also an important class of nanomaterials.
Nanomaterials have potential applications in the fields of
biotechnology, medical diagnostics, catalysis, high performance
engineering materials, magnetic recording media and adhesives.
These are metallic nanomaterials e.g., silver and gold nanoparticles
and nanorods. The optical properties of such particles depend on their
size and are intermediate between optical properties of the bulk material
and those of isolated chemical entities. In nanoparticles, a large
percentage of the atoms are in the surface rather than in the bulk phase.
Consequently, the chemical and physical properties of the material e.g.
electronic, magnetic and catalytic properties depend on the particle size
and shape. Metals absorb light primarily through electronic transitions. In
metal particles three types of transitions are possible namely:
(a) interband transitions (excitation of electrons from the filled valence
band to empty levels in the conduction band).
(b) intraband transitions (transitions within the conduction band), and
(c) the plasmon band (a collective oscillation of the conduction
electrons).
As the size of metal particles decreases to lengths smaller than the
electron mean free path (distance traveled by an electron between
successive scattering collisions with lattice centers), plasmon absorption
mode becomes more pronounced. The strong color of gold and silver
nanoparticles for example, originates from the excitation of the electrons
in the form of surface plasmon resonance. A sketch explaining surface
plasmon absorption is shown in Figure 1. It is shown that plasmon is a
collective excitation for quantized oscillations of the electrons in a metal.
A collective excitation, on the other hand, is a quantized mode in many-

6
body systems occurring because of cooperative motion of the whole
system because of interaction between particles. Plasmons as well as
phonons in solids are examples of collective excitations. Plasmon
absorption in spherical gold nanoparticles occurs at about 520 nm. This
absorption is absent for very small particles (2 nm and smaller) as well as
for bulk gold (of large particle size). Plasmon absorption of gold
nanoparticles originates from the oscillation of the free 6s-electrons of
the conduction band. (Gold has the electronic structure [Xe] 4f14 5d10 6s1).

Figure 1 A sketch explaining surface plasmon absorption. The electric field

E of the incident light induces polarization of the free surface electrons
with respect to the heavier ionic core.

Recently, sunlight mediated photochemical synthesis of nanoparticles

are more inspired than the existing methods because they are renewable,
nontoxic, and cost effective, minimum time consuming and synthesis size-
controlled NPs.

Materials
- Tetrachlorauric acid (HAuCl4.xH2O that is hydrogen tetrachloroaurate. It
is supplied in tri- or tetra-hydrated forms).
- Ammonium oxalate

7
Procedure
- Ammonium oxalate (100 mM) 800 g/L is added to a 100 mL conical flask
containing 40 mL of tetrachlorauric acid (1mM) and thoroughly mixed.
- Place the conical flask under bright sunlight for 20min whereby the pale-
yellow color solution turns into deep red color of gold nanoparticles
(AuNPs).

8
Experiment 4: Corrosion of Iron.

Objective:
To study the different processes occurring during rusting of iron

Discussion:
Rusting costs our society millions of pounds each year, not only
because of the need to protect iron and steel objects, but also because of
the expense involved in replacing rusted articles.
It is well known that rusting requires the presence of both oxygen
and water, but other factors (such as impurities in the iron surface,
availability of dissolved oxygen and electrolytes in the solution in contact
with the iron) can influence the rate of rusting considerably.
When rusting occurs, a hydrated form of iron (III) oxide with
variable composition (Fe2O3 . xH2O) is produced. This oxide is very
permeable to both air and water and it cannot protect the metal from
further corrosion, which continues unhindered below the rusted surface.
The process is represented in Fig. 1.
_
2e

Cathodic
water film area

2+
Fe
Anodic
area
Fe
Iron

Figure 1 Anodic and cathodic processes in the rusting of iron.

The corrosion process starts with the anodic reaction:

Fe ⎯⎯ →Fe2+ + 2e−
in which the ferrous ions leave the surface into the aqueous medium.

At the cathodic area, the following reaction occurs:

2e- + H2O + 1
→ 2OH-
O2 ⎯⎯
2

9
The resulting OH− ions then react with Fe2+ (produced at the anodic area)
giving Fe(OH)2
Fe2+ + 2OH− ⎯⎯ → Fe (OH)2
Further oxidation of the resulting ferrous hydroxide occurs giving rust:
dissolved O
Fe(OH)2 ⎯⎯⎯⎯⎯
water → Fe2O3 . xH2O
2

The rust is formed away from the metal surface thus it does not form a
protective layer in contact with the iron surface.
Acid conditions (low pH) accelerate rusting by promoting the
dissolution of iron. Electrolytes in the water and impurities in the iron also
assist the process by increasing the conductivity of the solution and
initiating cell action respectively. In industrialized areas, water on the
surface of the metal contains sulphur dioxide and this hastens rusting.
Sodium chloride from salt spray near the sea also does the same job.
To fight against corrosion, a sacrificial metal e.g., Zinc may be
connected to iron surface giving the so-called galvanized iron. Being more
electropositive, zinc is oxidized in preference to iron and zinc ions rather
than iron (II) ions pass into solution at the anodic region. Electrode
potentials confirm this fact.
E / volts
Fe(s) ⎯⎯→Fe2(aq)
+
+ 2e− + 0.44
Zn(s) ⎯⎯ → Zn2(aq)
+
+ 2e− + 0.76
Moreover, zinc on its own is protected from corrosion by a firmly adhering
layer of zinc oxide.
Another, yet less effective, method of protection is "tinplating" in which
iron sheets are immersed in molten tin. When the tin layer is scratched,
rusting occurs since iron is more electropositive than tin.
E / volts
Sn(s) ⎯⎯ → Sn2(aq)
+
+ 2e− + 0.14
Corrosion in pipelines made of steel is prevented by connecting
pieces of zinc or magnesium alloy to the buried pipeline at interval
distances. In oil refineries, magnesium alloys are bolted inside distillation
and cracking plant, so that these metals will corrode in preference to steel
and are replaced between regular maintenance inspections.

Apparatus
- A plastic dropper containing freshly prepared rusting indicator.
- Razor blades and other iron objects e.g. spoons, iron plates, ...... etc.

10
Chemicals
- Rusting indicator prepared by mixing 0.5 ml of 1% alcoholic
phenolphthalein solution with 3 ml of fresh potassium ferricyanide
solution and 100 ml of 0.1 N NaCl in water.

Procedure and Observations

Put a few drops of the indicator on the razor blades or the iron
objects and notice the development of color after a while (few minutes).
You will notice a deep blue spot close to the iron object (the anodic area)
due to the reaction between Fe2+ and potassium ferricyanide.
A pink color will develop at a spot that is away from the iron surface due
to the formation of hydroxyl ions that give pink color in the presence of
phenolphthalein indicator.

Report Form
The Corrosion of Iron

Name Id. No. :

Lab Section Instructor
Date : / /

The iron objects used are ,

The blue color on the surface is obtained much faster as
, ,

The resistance to corrosion goes in the order:

, ,

Questions:

 Write the anodic and the cathodic reactions in the process of corrosion
of iron.
 What is the structure of steel?
 Why does rusting of iron go faster in industrialized areas and at
seashores?

11
Experiment 5: Synthesis of iron oxide nanoparticles

(A) Synthesis of hematite nanoparticles

Preparation of nanoparticles of hematite ( α -Fe2O3 ) in water

Objective:
To prepare nanoparticles of the dominant hematite form
( α -Fe2O3 ) of iron oxide by a simple route of dropping FeCl3 solution
into boiling water. The nanoparticles are destabilized by adding
ammonium phosphate electrolyte.

Introduction:
Nanoparticles of iron oxides and their suspensions have extensive
applications in magnetic sealing, oscillation damping, and position
sensing, ultra-high density magnetic storage media, clinical diagnosis and
treatment and biological labeling, tracking, imaging, detection, and
separations. Their characteristics depend significantly on particle size,
particle morphology and size distribution.
Hematite, the most stable iron oxide, is of scientific and
technological importance as catalyst, pigment, ion exchanger, magnetic
material, lithium-ion batteries component and gas sensor. Hematite is an
antiferromagnetic semiconductor, the color of which varies with particle
size and aggregation form. The electrical properties of hematite can be
widely modified with some impurities. Further, it is a starting material for
the magnetic iron oxides used in magnetic recording tapes.
A simple method is described for the preparation of colloidal iron
oxide by drop wise addition of FeCl3 aqueous solution to boiling water.
A reddish colloidal solution of hydrated iron oxide was obtained that is
indefinitely stable. However, the characterization of such colloidal
systems is scarce and it needs a systematic elucidation of structure due
to its potential importance in various chemical and medical fields.
Colloids are intermediate states between suspensions (where
the size of the dispersed particles is large i.e., more than one micrometer
in diameter) and ordinary solutions containing simple molecules or ions
(i.e. less than one nanometer in diameter). Particles in colloidal systems
cannot diffuse through semipermeable membranes. They cause very
slight changes in the boiling or freezing temperatures of their dispersion
media.

12
 Colloidal particles do not stick together like suspensions due to
their small particle size and the presence of like-charges on their surfaces.
These like-charges repel each other keeping the colloidal particles
dispersed for long times. Some colloidal particles exist in the dispersed
state almost forever.
As an example, a red colloidal system is formed if FeCl3 solution is
added slowly to boiling water. This occurs because of a chemical reaction
in which the hydrated iron (III) ions lose water and hydrogen ions to form
a hydrated oxide, Fe2O3 x H2O that contains a variable amount, x,
of water of hydration. The equations for the change can be written as:

2Fe3+ + 3H 2O ⎯⎯
→ Fe2O3 + 6H +
Fe2O3 + x H 2O ⎯⎯
→ Fe2O3. x H 2O

3+
Fe
3+
Fe 3+
3+
Fe Fe
3+ Fe 2 O 3. x H 2O
3+ Fe
Fe

Fe 2 O 3. x H 2O 3+ 3+
3+ Fe Fe
Fe Fe
3+

Water
3+
Fe

As the particles of Fe2O3 begin to grow, they adsorb Fe3+ ions on

their surfaces, which makes them positively charged. Because each of the
oxide particles acquires the same electrical charge, they repel each other.
As a result, they no longer collide, so they stop growing. By the
time this has happened, they have reached colloidal size.
In aerosols such as smoke, the colloidal particles also pick up
electrical charges, but these tend to be from static electricity. These
particles do not stick together when they collide.
Colloids can be made unstable by countering the electrostatic
repulsion that stabilizes them.
Hydrated iron (III) oxide particles can be coagulated by adding an
electrolyte capable of neutralizing the charges on the surfaces of their
particles. The addition of a solution containing phosphate ion, for
example, will coagulate the sol just mentioned (A sol is one type of
colloidal systems in which the dispersed phase is a solid and the
dispersion medium is a liquid, see Table 1).

13
 Hematite ( α -Fe2O3 ), on the other hand, is antiferromagnetic. Half
the iron atoms have moments aligned in one direction and half in the
opposite direction. The forces virtually cancel each other out. There are
only a few minerals in this category and hematite is the most common.

Table 1 Types of colloidal dispersions

Dispersing Dispersed Colloid Type Examples
Medium phase
Solid Solid sol Pearls (‫)آلل‬
Solid
Solid Liquid Cheese, butter
emulsion
Gas Solid foam Pumice
Some paints, Starch in
Solid Sol, gel
water.
Liquid
Liquid Emulsion Milk (*)
Gas Foam Shaving cream
Solid Solid aerosol Smoke, dust
Gas Liquid
Liquid Clouds, mist, fog.
aerosol
*) Milk consists of very tiny drops of butter fat dispersed in an
aqueous phase that also contains casein (a protein) and a few other
ingredients.

Apparatus
- A Bunzen flame or an electric heater.
- A 250 ml beaker.
- A test tube
- A rubber or polyethylene dropper.

Chemicals
- A solution of ferric chloride (about one molar).
- Distilled water.
- Ammonium phosphate solution (about one molar).

Procedure
1- Heat about 30 ml of distilled water in a clean beaker until boiling.
2- While the water is boiling add ferric chloride solution drop by
drop and notice the resulting red color.
3- Leave the solution to cool down then pour some of the solution in

14
 the test tube.
4- Add drops of ammonium phosphate solution to the contents of the
test tube and notice the coagulation of the colloidal particles
following the combination with adsorbed Fe3+ ions.
5- Compare the product in step (4) with the solution left in step (3) and
notice the difference between the colloidal and coagulated forms
of iron (II) oxide.

Figure 2 shows the Transmission electron microscope (TEM) images

of iron oxide nanoparticles prepared by the above method that confirm
the nano-scale dimension of the prepared particles and shows that the
particles have an average diameter of about 6 nm.

Fig. 2 TEM of iron oxide nanoparticles. The bar to the left accounts for
50 nm

[Ahmed S. Al-Kady, M. Gaber, Mohamed M. Hussein, El-Zeiny M. Ebeid,

Spectrochim. Acta A Mol Biomol Spectrosc. 83 (2011) 398-405]

B- Synthesis of super paramagnetic iron oxide (SPIO) nanoparticles

Introduction
Nanoparticles of magnetite ( Fe3O4 ) with diameters in the 5-100
nm range are called superparamagnetic agents meaning they are
attracted to a magnetic field but retain no residual magnetism after the
field is removed. Therefore, suspended superparamagnetic particles
tagged to a biomaterial of interest can be removed from matrix using a
magnetic field, but they do not agglomerate (i.e. they stay suspended)
after removal of the field.

15
 Nanomaterials based on magnetic nanoparticles constitute a
rapidly evolving area in MRI contrast agents. As compared to the only
approved Gd-DTPA complex for human use so far. There are varieties of
magnetic nanomaterials available on the market for human use. These
nanomaterials are also called superparamagnetic iron oxide (SPIO). SPIO
agents are much more effective in MR relaxation than their Gd-DTPA
counterparts.
SPIO nanomaterials are promising contrast agents since their
properties may be fine-tuned for the specific application. They are non-
toxic and become rapidly cleared from the organism. Experiments have
been successful in receptor-specific SPIO delivery. The magnetic iron
oxide core is usually coated with shells that make them biocompatible
e.g. dextranes or siloxanes. Unlike contrast agents such as oils and fats,
superparamagnetic particles are miscible with aqueous systems allowing
their use in small amounts. This miscibility also allows them to be used
intravenously. Compared with Gd-DTPA, superparamagnetic materials
are much more potent (as much as 50 times more effective per mole).
Biomedical applications of iron oxide nanoparticles include retinal
detachment therapy, cell separation methods, tumor hyperthermia,
improved MRI diagnostic contrast agents and magnetic field-guided
carriers for localizing drugs or radioactive therapies. The nanoparticle
magnetic surface can influence both material durability and biological
environments and also toxicity issues.
Super-paramagnetic nanoparticles are currently used as magnetic
resonance (MR) contrast. They can be used as cellular contrast agents
allowing, for example, magnetic resonance tracking of magnetically
labeled progenitor cells following transplantation.
Magnetite ( Fe3O4 ) is a mixed oxide of the formula ( FO  Fe2O3 ). The
most common synthetic route to magnetite nanoparticles is the co-
precipitation of hydrated divalent ( Fe2+ ) and trivalent ( Fe3+ ) iron salts
in the presence of a strong base. First, we look at the preparation of iron
(II) chloride as a precursor to magnetite.

Preparation of magnetite ( Fe3O4 ) super-paramagnetic iron oxide

(SPIO) nanoparticles
Magnetite is a mixed oxide of the formula ( FO  Fe2O3 ). The most
common synthetic route to magnetite nanoparticles is the co-
precipitation of hydrated divalent and trivalent iron salts in the presence
of a strong base.

16
Procedure
Aqueous solutions of 0.1 M Fe(III) (30 ml) and 0.1 M Fe(II) (15 ml)
are mixed, and 3 ml of 5 M ammonia solution are added dropwise over 1
min with stirring on a magnetic stir plate. The stirring continues for 20
min under a nitrogen-gas atmosphere. The particles obtained are iron
oxide nanoparticle with yield, determined by weighing of the lyophilized
sample of the preparation, as 344 mg.
Magnetite ( Fe3O4 ), contains Fe2+ and Fe3+ ions with different
magnetic moments. The two networks of magnetic moments are
opposite but unequal, so that cancellation is incomplete and there is a
non-zero net magnetization. Such materials are called ferromagnetic
materials that can be separated from medium with the aid of an external
magnet as shown in Figure 3.

Fig. 3 Magnetite nanoparticles can be separated from medium with the

aid of an external magnet.
As an application, magnetite nanoparticles ( Fe3O4 ) were coated
with humic acids (HA) giving a novel low-cost magnetic sorbent material
for the removal of heavy metal ions from water. Nanomaterials are
potentially applicable to the remediation of industrial wastewater,
groundwater, surface water and drinking water. The main goal for most
of this research is to develop low-cost and environmentally friendly
materials for removal of heavy metals from water.

17
 For removal of metals from freshwater, 50 mg of the coated iron
oxide nanoparticles prepared by a co-precipitation procedure with cheap
and environmentally friendly iron salts and HA – was added into 100 mL
of water. Then the magnetic Fe3O4 /HA with sorbed heavy metals were
separated from the mixture with a permanent hand-held magnet.
Humic acids are a group of aromatic acids of high molecular mass
that are present in soils and can also be formed from peat and brown
coal or after refining sugar beet. Humic are related to the soil or water-
borne substances resulting from the partial decay of leaves, plant
material or any other organic waste. Humic acids (HA) are abundant in
natural aqueous systems, having skeletons of alkyl and aromatic units
that attach with carboxylic acid, phenolic hydroxyl, and quinone
functional groups. These functional groups have high complex capacity
with heavy metal ions. HA has therefore been applied to remove heavy
metal ions from water. The coating of magnetite nanoparticles with HA
greatly enhanced nanoparticle stability and heavy metal removal
efficiency of the nanoparticles.
Another application of magnetic particles is to attach them with
antibody. If the antibody finds a target antigen, then upon applying an
external magnetic field, the unbound species will tumble away. This
method avoids the time-consuming washing steps,
+yet it is sensitive.

N.B
There are five different kinds of magnetic behavior. The first of
these covers the most highly magnetic substances, like pure iron, and is
termed.
For removal of metals from freshwater, 50 mg of the coated iron
oxide nanoparticles – prepared by a co-precipitation procedure with
cheap and environmentally friendly iron salts and HA – was added into
100 mL of water. Then the magnetic Fe3O4/HA with sorbed heavy metals
were separated from the mixture with a permanent hand-held magnet.
To test the effect of time on the leaching of Fe3O4/HA
components and the sorbed heavy metals, Jiang and his colleagues
resuspended Fe3O4/HA laden with heavy metals in de-ionized water.
The results indicated that the leaching of both the sorbed heavy metals
and the material components were negligible.

"We also found that the removal of heavy metals by Fe3O4/HA was not
affected by the environmentally relevant parameters such as pH, salinity

18
and dissolved organic matter" says Jiang. "Furthermore, the proposed
procedure was very efficient as the sorption equilibrium was reached in
less than 20 min, and the Fe3O4/HA with adsorbed heavy metals can be
simply recovered from water with magnetic separations at very low
magnetic field gradients within a few minutes ".

This research is a good example of the ways nanotechnology can

be used to take substances that are abundant in nature (like iron oxide
and humic acid) and use them to synthesize novel, highly effective
adsorbent materials that are low-cost and have no adverse effect on the
environment. The result will not only be more effective and efficient
water treatment processes but also lower overall costs.

19
Experiment 6: Thermochemistry: determine the heat of precipitation by
simple calorimetry.

Objective:
To determine the heat of precipitation by simple calorimetry

Heat of precipitation of metals

The enthalpy change (H) for the displacement of one metal from
solution by another is measured calorimetrically in this experiment, e.g.
2+ 2+
Zn (s) + Cu(aq) ⎯⎯
→ Zn(aq) + Cu(s)
Apparatus:
- A balance (weighing to the nearest milligram).
- A Styrofoam or an expanded polystyrene cup (See Figure1)
- Thermometer, 0-50 C.

Figure 1 Apparatus for thermochemistry.

Chemicals:
- Standard 0.25 M copper sulphate.
- Zinc metal powder.
Weight roughly 0.02 mole of metal powder (an excess). Place a 50.0
3
cm aliquot of the salt solution in the polystyrene cup and measure the
temperature every minute for four minutes. The temperature should be
steady or show only a slow uniform change. On the fifth minute, tip in the
metal powder and stir continuously. Record the temperature every half

20
minute until a steady value has been observed for readings. The
replacement reaction should be completed in less than a minute.
Test your final solution for the absence of copper or silver ions. Any
deposit of metallic silver residues should be stored in a bottle.
Plot a graph of temperature against time. Extrapolate both straight
line portions of the graph to the fifth minute; the separation of the lines
at the fifth minute corresponds to a “corrected” temperature change for
the experiment (see Fig. 2). The extrapolation procedure compensates for
heat gains or losses from the surroundings.

Figure 2 Graph plotted to obtain a corrected temperature change.

From the temperature rise and the quantity of solution present,

calculate the number of joules liberated. The specific heat capacity of the
solution is approximately 4.2 J cm3 K-1 (note the unusual units since one g
of water nearly corresponds to one cm3).
From the quantity of solution present and the joules liberated, calculate
the molar heat of reaction in joules per mole of copper or silver atoms.
Interpret your results in terms of the electrochemistry series of the
elements.

This experiment can be further simplified as follows:

The heat change when a given metal reacts with copper (II)
sulphate solution is measured. The redox reaction that takes place is:
Zn(s) + CuSO4 (aq) ⎯⎯
→ ZnSO4 (aq) + Cu(s)
or
2+ 2+
Zn (s) + Cu(aq) ⎯⎯
→ Zn(aq) + Cu(s)

21
Chemicals and apparatus
- 100 cm3 of 0.5mol/l CuSO4(aq)
- About 3.5 g powdered zinc metal.
- An expanded polystyrene cup.
- Thermometer 0-100 °C.
Procedure
1- Place 20 Cm3 of 0.5 mol/l CuSO4(aq) solution in the expanded
polystyrene beaker and measure its temperature.
2- Tip into the solution enough powdered zinc to make sure that all the
Cu2+ ions are changed into copper metal (about 3.5 g powdered
zinc).
3- Record the maximum temperature reached and the temperature
change ∆T. (Atypical change in temperature is about ∆T= 24 °C).
4- Calculate the heat change of the reaction which is given by:
Heat change = mass × specific heat capacity × change in temperature
In this case we assume that the heat capacity of the mixture in the beaker
is equal to that of 100 cm3 of water which has a mass of 0.10 kg. The
specific heat capacity of water is 4.18 kJ kg-1K-1.
Therefore, we have
Heat change = 0.1 kg × 4.18 kJ kg-1 K-1 × ∆T °C = ………. kJ
Now this amount of heat is liberated when 0.05 mol of Cu 2+ are
precipitated as copper metal (100 ml of 0.5 mol/l solution). Therefore, the
heat change for 1 mol of Cu2+ ions is obtained by dividing by 0.05 mol.
Typical values would be as
Heat change =
10.03 kJ = 200.6 kJ mol-1
0.05 mol
This heat change is called the enthalpy change, ∆H, since the
reaction is performed at a constant pressure. Also, the convention is to
show exothermic enthalpy change as a negative number. So, finally we
have
∆ H = - 200.6 kJ mol-1

22
Experiment 7: Laser and X-Ray Diffraction

Objective:
To get a laser diffraction pattern using a grid and comparing it with
x-ray diffraction caused by crystals.

Discussion:
When a laser beam of suitable wavelength hits a grid, it undergoes
diffraction like x-ray diffraction on crystals. Both types of diffraction
undergo Bragg’s law in which:
n  = 2 d sin 
where: n is the order of diffraction,
 is the wavelength of the laser used, and
d is the spacings in the grid.
B
n=1

E
ser
d La
e
act
i ffr ~
~~

D ~
Laser A
>
~~

.
d D
. )
~
~

>
C O

Grid
Fig. 1 A laser diffraction setup

In Fig. 1, the extra-distance travelled by beam C E compared with

beam A B is the distance C D. This distance must correspond to integer
numbers of  / 2 i.e., CD = n

2
This allows the two beams to travel in phase and reach points B and E
giving the first order diffraction (n = 1).
CD = n
On the other hand, sin  =
d 2d
 n  = 2d sin .
By measuring the distance OE and the distance OC, we can get tan :
tan  = OE
OC
From this we get the angle , then sin .

23
In case of He-Ne laser,  = 632.8 nm.
Substitute in Bragg's law to get d1 value.
Measure the distance corresponding to the second order diffraction, and
obtain d2 value.
Take the average d value that corresponds to the spacings in the grid.

A similar analysis can be made for x-ray films. X-rays have short
o
wavelengths (in the order of 1.5 A , i.e., 0.15 nm) this makes them suitable
to study spacings in crystals.

Report Form
Laser Diffraction

Name Id. No. :

Lab Section Instructor
Date : / /

The distance OC = mm.

 for the laser beam = 632.8 nm = 632.8  10-6 mm
For n = 1
The distance OE = mm
OE
Tan 1= =
OC
1 = 
sin 1 =
From Bragg's law 1   = 2 d sin
d1 = mm.

For n=2
The distance OE = mm

OE
Tan 2= =
OC

2 = 
sin 2 =
d2 = mm.

24
 d1 + d2
Average d value = (mm)
2
= mm.
When x-ray photons hit crystals, an x-ray diffraction pattern -
similar to that obtained by laser diffraction - is obtained. The distance
between sample and the x-ray film is given as the diameter of film. Given
the following data, calculate the spacing d between atomic planes in the
given crystal. The distance between crystal and x-ray film is 28.6 mm and
the wavelength of X-ray CuK used is 1.54 Å, calculate the crystal spacing
a, b and c for the following x-ray diffraction patterns.

Questions:
 Can we use laser diffraction to study spacing in crystals? Why?
 What do we mean by constructive and destructive types of
interference? For the two beams AB and CE which type of interference
occurs such that a diffraction pattern occurs?
 Given we use two slits instead of the grid - what type of pattern should
we have?
 Why do we use the sign ( ) on some lines in the figure?
~
~

 What does the word L A S E R stand for?

 Why is it useful to use a laser beam in this experiment rather than other
sources of light?

25
26
Experiment 8: Atomic Weight of a Metal by Gas Evolution

Objective
To determine the atomic weight of zinc or magnesium metals using
gas evolution.

Discussion
The procedure of this experiment is based on the chemical reaction
between magnesium or zinc metals and hydrochloric acid to produce
hydrogen gas. The volume, pressure, and temperature under which the
hydrogen is collected will be measured. From the known quantity of
magnesium or zinc used and the stoichiometry of the reaction (balanced
equation), the number of moles of hydrogen produced can be calculated.
Since the hydrogen is collected in a measuring cylinder over an
aqueous solution (see the following procedure), the gas pressure in the
cylinder after the reaction has ceased is the sum of the hydrogen gas
pressure and the vapor pressure of water. In order to obtain the pressure
of the hydrogen gas, the vapor pressure of water, PH2O , at the
temperature of the measurement (taken from Table 1), must be
subtracted from the atmospheric pressure, Patm . Thus, the pressure of
the hydrogen is given by PH2 = Patm − PH2O
In case the liquid levels (step 3) cannot be equalized after the
reaction has ceased, a further correction will be required since the
pressure of the gases in the cylinder (hydrogen and water vapor) will not
then be equal to the atmospheric pressure. If this is the case, the
difference in levels must be measured as accurately as possible. This
difference, which represents the desired pressure difference, must be
converted to mmHg.
Suppose that h is the height of the column of liquid inside the
cylinder in mm that exists above the level of water in the beaker. This
corresponds to a pressure of h/13.6 mm Hg since the ratio of the densities
of Hg and the aqueous solution inside the cylinder is approximately 13.5:
1. This gives the reduction in pressure due to the hanging column of
solution inside the cylinder ( Pcolumn ).
This pressure must be subtracted from the atmospheric pressure.
Thus, if the levels cannot be equalized the pressure of hydrogen must be
obtained from
PH2 = Patm − PH2O − Pcolumn

27
Procedure:
1- Calculate the mass of zinc necessary to evolve about 50 ml of H2 at STP.
Then weigh approximately this quantity of zinc on the top-loading
balance to the nearest mg.
2- Add approximately 50 ml of concentrated HCl to a 100 ml measuring
cylinder with your wash bottle, wash down into the cylinder any acid
that might have adhered to the walls. Fill the cylinder with water and
invert into a beaker nearly filled with water. Clamp in position (Figure
10). Put the piece of zinc into the beaker filled with water where it sinks.
Adjust the mouth of the measuring cylinder such that the piece of zinc
becomes inside the mouth of the measuring cylinder.
3- The concentrated HCl will gradually diffuse down to the Zn and react
with it. After the reaction has ceased, if possible, adjust the liquid level
in the cylinder to the level of liquid in the beaker. The gas pressure in
the tube is then equal to atmospheric pressure. If the difference in
levels is very large it must be measured as shown in Figure 1.
4- After temperature equilibrium is attained, record the temperature of
the water in the beaker. Take this value as your gas temperature.
5- Calculate the volume of hydrogen VH2 and the height of column h mm
as shown in Fig. 1.
6- Calculate the corrected pressure for the experiment as described
above.
7- Calculate the corrected volume (V) in your experiment at standard
conditions i.e. P = 760 mmHg and T = 273 Kelvin:
PVH2 760V
=
T 273
8- Determine the number of moles of hydrogen evolved knowing that
each mole of a gas occupies a volume of 22400 ml at standard
conditions. The number of moles of hydrogen = V/22400 this equals the
number of moles of zinc since the reaction between hydrogen and zinc
occurs in mole to mole.
9- The number of moles of zinc = weight of zinc /atomic weight. Knowing
the number of moles of zinc and the weight of the zinc sample used one
can determine the atomic weight of the metal.

28
Figure 1 Collecting a gas with the use of an inverted measuring cylinder.

Report Form
Atomic weight of a metal by gas evolution
Name Id. No. :
Lab Section Instructor
Date : / /

Gas temperature C
Mass of Zn g
Volume of gas ml
Height of column mm
Vapor pressure of water mm Hg
Pressure of column mm Hg
Corrected pressure mm Hg
Corrected volume (V) ml
Number of moles of H2 =
V = mol
22400
Number of moles of Zn mol
Atomic weight of Zn amu or g/mol
(amu stands for atomic mass unit)

29
Sample Calculations

Questions:

 Suppose that your sample of metal had been partially oxidized before
you started the experiment. How would this affect your calculated
equivalent weight?
 Suppose that you did not wait long enough before getting the final
temperature reading, and the temperature of the gas was higher than
the temperature of the water. How would this affect your calculated
atomic weight?
 How many electrons were transferred in oxidizing your sample of
metal?
 How do you determine the pressure of the gas inside the measuring
cylinder after the reaction?
 In a typical experiment of this kind, it is observed that 0.1362 g of metal
liberates 33.6 ml of hydrogen gas at 23 C and 0.982 atm barometric
pressure. What is the atomic weight of the metal?
 Suppose that you used dilute phosphoric acid (H3PO4) instead of
hydrochloric acid (HCl) in this experiment. What difference would it
make in your results?

Table (1): Vapor pressure ( PH2O ) of water at various temperatures

P,
t, C P, mmHg t, C P, mmHg t, C P, mmHg t, C
mmHg
13.0 11.2 19.0 16.5 25.0 23.8 31.0 33.7
14.0 12.0 20.0 17.5 26.0 25.2 32.0 35.7
15.0 12.8 21.0 18.7 27.0 26.7 33.0 37.7
16.0 13.6 22.0 19.8 28.0 28.3 34.0 39.9
17.0 14.5 23.0 21.1 29.0 30.0 35.0 42.2
18.0 15.5 24.0 22.4 30.0 31.8 36.0 44.6

30
Experiment 9: Study of Heating and Cooling Curves; Changes of State.

Objective:
To study the cooling curve of a fused salt and to apply the phase
rule to that curve. The meaning and energetics of disordered supercooled
states will also be highlighted.

Discussion:
When sodium acetate trihydrate ( CH3COONa.3H2O ) is heated and
the sample temperature is followed as a function of time, a heating curve
is obtained. When the sample is heated, its temperature increases
gradually until it starts to fuse at point (B) in Fig. (1). The temperature
remains constant during the process of fusion until point (C) where the
whole solid changes into liquid. At point (C) the temperature starts to rise
again. The amount of heat needed to fuse one mole of the sample is
known as the “latent heat of fusion”.

Figure 1 The heating curve of sodium acetate trihydrate

If we start with a fused sample (at 80 C for example) and follow

the decrease in its temperature as a function of time, we'll get a “cooling
curve” of nearly the same behavior as shown in Fig. (1) with a possible

31
exception that a “supercooled state” or a metastable phase may be
obtained as shown in Fig. (2).

Figure 2 The cooling curve of fused sodium acetate trihydrate

The British firm “Altic Edeco Ltd” applied this principle in 1988 to
produce heat batteries that are currently marketed and used in safe
heating of baby beds, making use of emitted heat in power stations,
military purposes like diverting the heat seeking missiles, deicing and in
rescue operations.

Apparatus:
- A test tube with thermometer as shown in Fig. (3)
- A hot plate or a Bunzen flame.
- A 250 ml beaker containing about 200 ml of hot water (at ca. 80 C)
used as a water bath.
- A burette stand and clamp.

32
Chemicals:
Sodium acetate trihydrate crystals are transparent crystals. The
anhydrous form ( CH3COONa ) is a white material and will not work in this
experiment.
If hydrated sodium acetate were not available, the anhydrous
sample would be recrystallized from water. The isolated crystals in this
case are in the hydrated form.
Other salt hydrates may be studied e.g., sodium sulphate
decahydrate Na2SO4 10H2O giving transition at 32.3C or sodium
bromide dihydrate NaBr.2H2O

Procedure:
1- Put sodium acetate trihydrate sample in the test tube (to a height
of about 3cm). Some crystals are kept aside for possible use at the
end of the experiment.
2- Immerse the thermometer bulb in the crystals.
3- Suspend the test tube with its contents vertically in the 250 ml
beaker containing about 200 ml water.

Thermometer

Fused sodium
acetate trihydrate

Figure 3 Apparatus used in following the cooling curve of sodium acetate

trihydrate.

4- Heat the beaker until sodium acetate trihydrate fuses. Continue

heating until the thermometer reading is about 80 C.
5- Remove the heater to allow the sample to cool and start recording
the temperature as a function of time. Carry on taking readings until
the room temperature or close to it.

33
 6- Don’t throw away any samples since they will be reused by other
students.
7- If you have a “supercooled state” (i.e., the sample does not
crystallize even at room temperature) add one crystal of the sample
where solidification occurs with a sudden increase in sample
temperature.
8- Plot the time (as x-axis) versus temperature (as the y-axis) and
record the solidification temperature.

Application of the phase rule to the cooling curve

The phase rule (also known as Gibb’s phase rule) is written in the
form:
P+F=C+E
Where P is the number of phases. We mean by a phase whether the
sample in solid, liquid, gas phases or in a certain crystalline form.
F is the number of degrees of freedom that are the least number of
independent variables defining the state of a system (e.g. pressure,
temperature, composition, etc.) that must be given definite values
before this state can be completely defined.
Under working conditions in laboratories, pressure is considered fixed.
C is the number of chemical components in the system.
E is the number of environmental (or external) variables.
Under ordinary conditions E = 1 to account for temperature (since
pressure is fixed in this case).

Taking E = 1, then the phase rule is written as:

P+F=C+1
or
F=C-P+1
We are going to apply this rule to the cooling curve of sodium acetate
trihydrate.
In the region, A B (refer to Fig. 6), the number of components C = 1
The number of phases P = 1 since we have only liquid.
Then F = C - P + 1
=1-1+1=1
This means that we have one degree of freedom, that is temperature. This
means that temperature can be varied within this region.

In the region B C D
C=1

34
P = 2 since we have a liquid and a solid that separates in this region.
F=C-P+1=1-2+1=0
This means that no degrees of freedom are left, and temperature does
not change in this region.
In the region D E, we have a solid only i.e.
P=1
Then F = 1, we’ll still have one degree of freedom thus temperature varies
in this region.

Report Form

Study of Heating and Cooling Curves

Time (min.)
Temp. (C)

Time (min.)
Temp. (C)

Time (min.)
Temp. (C)

Time (min.)
Temp. (C)

From the cooling curve

The solidification temperature is ……………………… C.
Have you obtained a supercooled state?

Yes ( ) No ( )

35
36
Example
Compare between the heat stored in one liter of a heat battery at 20 C
and a liter of water at 58 C given the following:
• The specific heat capacity of water is 4.2 J g-1 C-1
• The latent heat of fusion ΔHf of the heat battery is ΔHf = 263 Jg-1
• The density of the heat battery is 1.45 g/cm3.

Solution
For one liter of water:
The heat content = mass × specific heat capacity × T
= 1000 × 4.2 × (58-20) = 159.6 kJ
For one liter of the heat battery
The mass of one liter of heat battery = 1450 g/l.
The heat content in one liter of heat battery = 1450 × 263
= 381.350 kJ.
Questions:
 What is the difference between fusion and melting?
 What would be the mathematical expression of Gibbs phase rule if the
pressure of the experiment was also variable?
 In the following change
(1) Fusion
Solid (2) Crystallization
Liquid

which of the processes (1) and (2) is endothermic and which is

exothermic? Why?
 Why does solidification of the supercooled state occurs upon addition
of one crystal of sodium acetate trihydrate? Why is heat evolved upon
solidification?

37
Experiment 10: Miscibility as a Function of Temperature.

Objective:
To study the miscibility of water/ phenol system as a function of
temperature and apply the phase rule to such a system

Discussion:
When two liquids are mixed, one of the following cases may arise:
(a) The two liquids are completely miscible at all proportions yielding one
homogeneous liquid e.g., ethanol and water.
(b) The two liquids are partially miscible yielding either one or two liquid
phases, depending on the conditions e.g., phenol and water.
(c) The two liquids are immiscible, always yielding two distinct phases
under ordinary conditions e.g., carbon tetrachloride (CCl4) and water.

The mutual solubility of partially miscible liquids usually increases

with temperature. In this case, the solubility curve exhibits a maximum at
the “critical solution temperature” above which the two liquids become
completely miscible at all proportions. For some liquid pairs such as ether
and water, the mutual solubility decreases with temperature and the
solubility curve shows a minimum at the critical solution temperature
below which the two liquids become completely miscible at all
proportions.

The mutual solubility of chemicals is a very important phenomenon

in many areas e.g. synthetic chemistry, industry ...... etc. The solubility of
reaction products in the reaction media lowers the yield of the reaction.
Some products may contain solvent molecules and should be dried.

Apparatus
- Two burettes
- Six clean and dry test tubes (of length 15 cm and internal diameter
about 2.5 cm).
- A beaker (250 ml) half-filled with water and is used as a water bath.
- Bunzen flame or a hot plate.
- Thermometer (0-100 C).
- Six small wires for stirring the mixtures.

38
Chemicals
A solution of phenol in water of concentration 80% (w/w) is
prepared by dissolving 100 g of phenol in 25 ml of distilled water.

Caution: phenol is a poisonous corrosive material.

Procedure
1. Fill the two burettes, one with distilled water and the other with the
above phenol solution.
2. Prepare six mixtures by carrying out the additions shown in Table (3).
3. Heat gradually while the mixture is constantly stirred until the
turbidity disappears. Record the temperature at which the turbidity
disappears. Take the test tube out of the water bath, keep stirring the
clear mixture and record the temperature at which turbidity just
appears again. These two temperatures should be nearly the same,
and their mean value gives the miscibility temperature of the mixture
used.

Table (3) Composition of water-phenol samples.

Mixture No. vol. of 80% phenol volume of water phenol % (w/w)

1 8 ml 2 ml 63.5
2 6 ml 4 ml 49
3 5 ml 5 ml 41
4 4 ml 6 ml 33
5 2 ml 8 ml 16.7
6 1.5 ml 8.5 ml 12.6

 Repeat step () with all the mixture samples and record the
miscibility temperature.

Calculations
 Calculate the percentage of phenol (w/w) in each of the above
mixtures.
 Plot the percentage of phenol (w/w) as the x-axis against the
miscibility temperature as the y-axis.
 From the curve obtained, find out the critical solution temperature
(Tc) and the corresponding composition.

39
Additional Tests
We can examine the salting out phenomenon, that is the effect of
materials that dissolve in one of the liquids e.g. sodium chloride that
dissolves in water and not in phenol. This raises the critical solution
temperature Tc. To carry out this test, 0.1M sodium chloride is used
instead of distilled water.
We can also examine the effect of materials that dissolve in both
liquids. Oxalic acid can be used in this case. If we use 0.1M oxalic acid to
replace distilled water, we’ll notice a decrease in the TC value.
In these cases, NaCl delays the miscibility (since it dissolves in one
only of the liquids) whereas oxalic acid enhances miscibility due to its
solubility in both solvents.
The temperature-composition diagram of the phenol-water system
is shown in Fig. (1).

o
Temp. C

C
A

H2 O Phenol
% Phenol (w/w)
Figure 1 Temperature-composition diagram of phenol-water system.

Outside the area bounded by the curve ABC there occurs one
unsaturated homogeneous liquid phase. Within that area, two liquid
phases in equilibrium with each other coexist; one is water saturated with
phenol and the other phenol saturated with water. Any point on the curve
represents one saturated homogeneous phase.

40
 By applying the phase rule, then for the area outside the curve ABC,
the number of components equals 2, the number of phases equals one,
and then the number of degrees of freedom F is obtained from the phase
rule as follows:
F=C-P+1
=2-1+1=2
This means that we have two degrees of freedom. This means that
we can vary the temperature and composition independently in this
region. For any point contained within the curve, the number of phases in
two and the number of degrees of freedom F is given as:
F=C-P+1
F=2-2+1=1
This means that we have only one degree of freedom. This means that if
we change the temperature independently, the composition will
automatically change and vice versa.

Note (1):
A suitable pair of liquid is glycerol and m-toluidine. The following
mixtures are made up by weighing the glycerol into tubes and adding the
m-toluidine from a burette.

Table (3)
Mixture No. Glycerol (g) m-Toluidine (ml)
1 4 25
2 5 25
3 6 25
4 10 35
5 10 20
6 20 10
7 6.6 2
8 6 1.5
9 9.9 2.2

41
Note (2):
The tie- line principle
The tie - line principle is a simple method that is usually applied to
obtain the composition and relative proportions of different phases of a
particular sample at a given temperature.

Temperature

A C
t oC B

X Y Z
Composition
Figure 2 Application of the tie-line principle.

Thus, with reference to Fig. 2, at temperature t C, a sample having

composition Y exists as two layers A and B. Layer A has the composition X
and the layer B has the composition Z. The relative proportions of A and
B in sample C is given by weight as:
A = BC
B AC
where AC and BC are the lengths (in mm or cm) of the lines AC and BC
respectively.

42
Report Form
Miscibility as a Function of Temperature

Name Id. No. :

Lab Section Instructor
Date : / /

The liquids used are and

Composition
Miscibility
temperature
C

The critical temperature is C

By applying the tie-line principle, a mixture of composition 55%
phenol at 50C is composed of two phases A and B. The
compositions of these two phases are:
A = ……………….. % phenol
B = ……………….. % phenol
The ratio of these two phases is:
A = BC
B AC

43
44
Questions:
 Why does NaCl dissolve readily in water and not in phenol?
 What do we mean by having one degree of freedom inside the
boundary curve in water-phenol system?
 What causes the immiscibility of some other pairs?

45
Experiment 11: Volume Changes upon Mixing

Objective:
To observe the phenomenon of volume changes upon mixing of
different liquids caused by changes in intermolecular forces.

Discussion:
When two liquids are mixed, the volume of their solution may be
less or greater than the sum of their individual volumes.
A mixture of 50 ml of absolute ethanol with 50 ml of water has a
volume of about 96.5 ml at 20C. (The error in the final volume for the
experiment is  0.2 ml). The effect is nearly the same when methanol is
used. If 95% ethanol is used, the volume of the mixture will be 96.8 ml.
The structure of liquid water is open because hydrogen bonds
between the molecules hold them in specific orientations to each other.
This open ice-like structure is broken by introducing ethanol, resulting in
a compacting of the solution relative to the pure liquids.

Procedure
In a clean 50 ml burette add 25 ml of distilled water. Add absolute
alcohol or 95% methanol or ethanol very slowly on the wall of the burette
so as to avoid mixing the alcohol with water as much as you can. Continue
adding alcohol slowly until the 50 ml reading. Close the top end of the
burette with your finger and invert the burette upside down several times
for proper mixing. Report the volume of the mixture and notice that it is
less than the original reading when the two liquids were not properly
mixed.
Keep the mixture for the next experiment entitled the salting out
of ethanol and water.

46
Experiment 12: The Salting out of Ethanol and Water *

Objective:
To illustrate the principle of salting out which is based on
intermolecular forces.

Discussion:
Salting out is the precipitation of a dissolved substance by addition
of another (usually a salt) that lowers its solubility. This method is
commonly used by biochemists in the purification of proteins. In the
process of salting out, weak intermolecular forces e.g., hydrogen bonds
are overrun by solvation of electrolytes. In this experiment, water and
ethanol, which are soluble in all proportions i.e., totally miscible are made
immiscible by the addition of potassium carbonate.

Chemicals:
- 10 ml ethanol.
- 10 ml water
- or use 20 ml of the mixture obtained in the preceding experiment
entitled “volume changes upon mixing.”
- 3 g potassium carbonate.
- Few drops of phenolphthalein indicator.
- A drop of 1 M hydrochloric acid.

Apparatus:
- 50 ml graduated cylinder.

Procedure:
1- Mix ethanol, water, pH indicator and HCl in the cylinder to form a
single colorless solution.
2- Add 3 g solid potassium carbonate and shake well to dissolve solid
potassium carbonate.
3- Notice that the solution turns red and separates into two phases: a
colorless aqueous layer and a red organic phase. The pH indicator is
more soluble in ethanol. The color change of the pH indicator is
attributed to the fact that potassium carbonate acts as a base.

47
Experiment 13: The Catalytic Decomposition of Hydrogen Peroxide.

Objective:
To study the kinetics of catalytic decomposition of hydrogen
peroxide using gas evolution.

Discussion:
Hydrogen peroxide is a liquid of boiling point 150.2 C and is usually
sold as a solution in water. Its concentration is usually expressed in
volume (volume strength) where a 10-volume solution, for example,
means that a certain volume of H2O2 solution gives ten times that volume
of oxygen at standard temperature and pressure. Ten volumes H2O2 is
approximately 3% w/v.
Hydrogen peroxide decomposes to water and oxygen according to
the following equation:
→ H2O + 1 O2 
H2O2 ⎯⎯
2
This reaction can be catalyzed with manganese dioxide MnO 2,
platinum or iodide ions in non - acidic media.
In non - acidic media, the following catalytic reaction occurs:
I-→ H O + 1 O (g) 
H2O2 (aq) ⎯⎯ 2 2 2
[In acidic medium, the following reaction with iodide occurs:
2H+ + 2I- + H2O2 ⎯⎯ → 2H2O + I2
Even sealed and refrigerated hydrogen peroxide decomposes with time.

Caution: concentrated hydrogen peroxide can cause burns. Always wear

goggles and neoprene, butyl rubber, or vinyl gloves when handling the
reagents.
In this experiment, the decomposition of hydrogen peroxide is
catalyzed by iodide ( I- ) releasing oxygen with the production of soap
bubbles (*). This demonstration is known as “Elephant’s Toothpaste” as
done by the Weird Science Group from Illinois.
The decomposition of hydrogen peroxide follows first order kinetics
in which the rate of reaction is given as follows:
- dc / dt = k c (1)

(*)
A.R. Conklin, Jr. and A. Kessinger, J. Chem. Educ. 73 (1996) 838.

48
where c is the concentration of H2O2 at time t and k is the first-order rate
constant.
n
[The general rate equation is - dc / dt = kc where n is the order of
reaction and equals one in the present reaction].
The negative sign is introduced since the concentration decreases with
time.
Rearranging equation (1) gives:
- dc/c = k dt
Integrating between the limits c = co at zero time and c = c at time t gives:
c t
−  dc = k  t dt
co 0
− lnc = kt + constant
−lnco = 0 + constant i.e. the constant = −lnco
ln co - ln c = kt
ln(co / c) = kt (2)
Equation (2) is known as the first-order kinetic equation and is given also
in the form:
a
ln =kt
a−x
where: a is the initial concentration of reactant,
x is the amount reacted up to time t.

The half - life period (t1/2)

The half - life period is the period required by the reactant to reach
half its original concentration.
1
At t1/2 , c = co
2
ln co/c = ln 2c/c = ln 2 = 0.693 = kt1/2
t1/2 = 0.639/k (time)

Apparatus
- A 100 ml measuring cylinder.
- A burette

Chemicals
- 5 ml of 5% hydrogen peroxide solution.
H2O2 content in as-received samples is 30 - 32 %. Dilution can be
performed using the dilution relation:

49
 CV = CV
Where C and C are concentration before and after dilution, V and V are
the volumes of the concentrated and dilute samples respectively.
(Note: Ten volume H2O2 is approximately 3% w/v).
- 0.2 ml of saturated potassium iodide (to be added from a burette)
- colorless liquid washing detergent
Procedure
1- In a 100 ml graduated cylinder, add about 5 ml of 5% H2O2 solution, two
or three squirts of liquid dish washing detergent.
2- Swirl the contents of the cylinder and quickly add 0.2 ml of saturated
potassium iodide solution before the agitation has subsided. Record the
time.
3-Record the amount of foam produced in cm3 at different time intervals
and tabulate your results as follows:

Time (seconds) 
Volume of foam (ml) 90

The amount of foam at the end of the reaction under these working
conditions is 90 ml at 22 C.

Calculations
1- The total amount of foam produced corresponds to the total amount
of H2O2 (a).
2- The amount of foam at time t corresponds to the amount reacted of
H2O2 (x).
3- From (1) and (2) we can get the amount of foam corresponding to (a-
x).
4- Tabulate your results as follows:

a a
Time (sec.) a-x ln
a−x a−x

a
5- Plot the time as the x - axis versus ln as the y - axis.
a−x
-1
6- The slope of the resulting curve gives the rate constant k (sec ).

50
7- Calculate t1/2 from the relation:
t 1/2 = 0.693/ k (sec.).
N.B. Approximately the same volume of foam is produced when
potassium iodide is substituted for sodium iodide. However, no reaction
takes place when potassium chloride or potassium bromide is used. This
demonstrates that it is indeed the I- anion which is the effective catalyst
for this reaction.
The effect of temperature can also be investigated. At higher initial
temperatures, more foam is produced.

Report Form
The Catalytic Decomposition of Hydrogen Peroxide
Name Id. No. :
Lab Section Instructor
Date : / /

V = a = ml
Temperature = C

a a
Time (sec.) Volume of foam (ml)= x a-x ln
a−x a−x

51
52
53
Example
32
P is much used as a radioactive tracer in biochemical and genetic
studies. It decays by  − emission with a half-life of 14.2 days. Cell
hydrolysates containing 0.8 curies of 32P were to be disposed of as waste
once their total radioactivity had decreased to an acceptable level of 10-5
Ci. Calculate the period for which radioactivity would have fallen to this
level.

Solution
Since radioactive decay is a first - order process,
t1/2 = 0.693/k
Thus, for 32P, the rate constant k is given as
k = 0.693/14.2 = 0.0488 day-1
The kinetic equation for this first - order reaction is
a
ln = kt
a−x
Taking a as the initial concentration of 0.8 Ci and (a - x) as the final
concentration of 10-5 Ci, then
ln (0.8 / 10-5) = 0.0488 t
t = 231. 5 days
Thus, the cell hydrolysates should be disposed after storing for 231.5 days.

Example
A reaction following first - order kinetics of t1/2 = 30 mins. Calculate
the time necessary for 90% completion of this reaction.

Solution:
At 90% completion and supposing a = 100, then (a-x) = 10.
For first-order reactions:
t1/2 = 0.693/k
0.693
30 = , k = 0.0231 min-1
k
a
ln = kt
a−x
ln 100 = 0.0231 t
10
2.303 log 10 = 0.0231 t
t = 99.7 mins.

54
Experiment 14: Kinetics of the Reaction between Iodide and Hydrogen
Peroxide in an Acidic Medium.

Objective:
To measure the rate of reaction between iodide ion and hydrogen
peroxide in acid solution, keeping the concentration of hydrogen ions and
iodide ions constant

Discussion:
The reaction investigated in this experiment is:
2H+ + 2I- + H2O2 ⎯⎯ → 2H2O + I2
The rate of this reaction depends on the concentration of all three
species appearing on the left - hand side of the equation. By keeping ( H+
) and ( I- ) virtually constant during a given run, it is possible to investigate
the order with respect to ion alone. The concentrations ( H+ ) and ( I- ) are
kept approximately constant simply by having a large excess of both ions.

The rate of the above reaction can be expressed as the rate of decrease
of the concentration of H2O2 that is given as:

-d[H2O]
Rate of reaction = = k(H+ )p (I− )q (H2O2 )r
dt

The constant k is called the rate constant.

The exponent p is called the order of reaction with respect to H+ ; likewise
for q and r.
The sum (p + q + r) is called the overall reaction order. It is very important
to realize that p, q and r cannot be predicted from the law of mass action
but can only be determined experimentally.
Taking excess concentration of H+ and I- , these concentrations are
considered constant along the reaction and it was found that the reaction
is first order with respect to H2O2 , then we can write

d[H2O2 ]
- =k[H2O2 ]1 = k [H2O2 ]
dt
Where k is known as the observed rate constant
k = k[ H+ ][ I- ]

55
Taking the initial concentration of [ H2O2 ] as (a) mol / l and the
concentration at time t as (a-x) mol / l, then
ln a = kt
a−x
This equation is a first - order kinetic equation. A plot of ln
a
a−x
against time gives a straight line of slope k .

Students can be provided with the volume of 1.0 M sodium

thiosulphate equivalent to 25 ml of ( H2O2 ) solution. This corresponds to
(a) and can be determined as follows:
Dissolve a few grams of potassium iodide in a little water in a
conical flask, add a few ml of 10 M sulphuric acid (Take care - heat is
evolved) and while the solution is still warm pipette in 25 ml of peroxide
solution. Iodine is formed. The reaction is complete very quickly since the
concentrations are very high. Crystals of solid iodine may from but will
dissolve during the titration. Titrate against the thiosulphate; no indicator
is required.

Chemicals
- 0.1 M potassium iodide (KI)
- 2 M hydrochloric acid (HCl)
- 2 M sodium chloride (NaCl)
- starch solution
- 1M sodium thiosulphate (Na2S2O3)
- 5 volumes hydrogen peroxide ( H2O2 )
- 10 M sulphuric acid (H2SO4)

Apparatus
- 250 ml reagent bottle
- Graduated pipette (10 ml)
- Graduated cylinder (100 ml)
- 25 ml burette

Experimental
1- In a 250 ml reagent bottle mix the following:
25 ml of 0.1 M KI
50 ml of 2 M HCl
2.5 ml of 2 M NaCl
150 ml of water

56
 0.5 ml of starch
(NaCl and starch solutions are taken using a pipette and KI, HCl and
water are taken using a measuring cylinder)
2- Add 1.5 ml of 1 M thiosulphate.
3- Add 25 ml of (H2O2) starting the clock when half has run in. Stir
vigorously until all the peroxide has been added and watch for the blue
color to appear. This will occur when enough iodine has been produced
to react with the 1.5 ml M thiosulphate.

Note the time at which the color appears and immediately add a
further 1.0 ml thiosulphate, stirring until the blue coloration disappears.
Note the time at which the color reappears, add a further 1 ml shot of
thiosulphate. Continue this until a total of 10.5 ml of thiosulphate has
been added.
(N.B. the clock should run continuously - the reaction producing the
iodine does not stop while the solution is colored. This also means that if
you are slightly late with one shot of thiosulphate, it will still "catch up"
so that the next appearance of color will be on time.)
Some heat evolves in the reaction; keep a periodic check on the
temperature of the mixture and make a record of it.

Treatment of results
The total number of moles of thiosulphate consumed at a given time
must equal twice the number of moles of iodine and consequently the
peroxide reacted up to this time (x):
I2 + 2S2O3− ⎯⎯ → S4O6−− + 2I−
- Calculate (a-x) that is [ H2O2 ] against time t where (a) is the initial
concentration of H2O2 and x is the amount reacted at time t . The
remaining concentration at time t is (a - x).
a
- Test the first-order kinetic equation by plotting ln against
a−x
time t. From the slope determine the observed rate constant k .

N.B.
- Sodium chloride is added to keep ionic strength constant along the
reaction.
- Direct thiosulphate volumes can be used to verify the validity of the
first order kinetic equation.

57
Experiment 15: Molecular Weight of a Polymer from Viscosity
Measurements.

Objective:
To determine the molecular weight of a polymer from viscosity
measurements

Discussion:
The ratio of the viscosity  of a solution of non-spherical high
polymer molecules to the viscosity 0 of the solvent is related to the
molecular weight, M, of the polymer by the expression:
( /  ) − 1
= KM (1)
c
In this equation K is a constant for any given type of polymer, solvent, and
temperature,  is a function of the geometry of the molecule, and c is the
number of grams of polymer in 100 ml of solution. The term (/o) -1 is
known as the specific viscosity sp; equation (1) may therefore be written
in the from
sp
= KM (2)
c
This equation is only valid for very dilute solutions (less than 1
percent) and hence the graph which is drawn of sp /c vs. c is
extrapolated to zero concentration. The extrapolated value is known as
the intrinsic viscosity [], i.e.
sp
[] = lim (3)
c→0 c
The intrinsic viscosity is therefore the intercept on the graph of sp
/c vs. c as shown in Fig. 1.

sp
c


 

c
sp
Figure 1 A Plot of c vs. c for dilute polymer solutions.

58
 The [] value obtained by this method may then be used to
determine the molecular weight of the polymer by applying the equation
[] = KM (4)
where M is known as the viscosity average molecular weight and K and 
are constants. The constant  is a function of the geometry of the
molecule in solution and varies from about 0.5 for curled polymer
molecules, the so-called random coils, to about 1.7 for rigidly extended
molecules. The constants  and K depend on the type of polymer, the
solvent, and the temperature of the viscosity measurements. They are
determined by measuring the intrinsic viscosity of polymers for which the
molecular weight has been determined by an independent method.
For polystyrene in toluene at 25C,
 = 0.62 and K = 3.7  10-4
for polymethylmethacrylate in chloroform,
 = 0.85 and K = 3.3  10-5
for polyvinyl chloride in cyclohexane at 25C,
=1 and K = 1.0 x10-5
and for polyvinyl alcohol in water at 25C,
 = 0.76 and K = 2.0 x 10-4

Apparatus and Chemicals.

Viscometer, stopwatch, 50 ml volumetric flasks, graduated pipette,
polyvinyl alcohol and distilled water.

Experimental:
Thoroughly clean and dry the viscometer with acetone and air.
Prepare a solution of the polymer by dissolving about 0.05 g in 25 ml of
water. Determine the flow times at room temperature for the solvent and
for the solution. Repeat the procedure so that determinations are made
1 1 1 1
at dilution factors of , , , , and
1 of the concentration of the
2 3 4 5 6
original solution.

Treatment of results:
Since the measurements are made with one viscometer, the
viscosity ratio of the solution and solvent is given by:
 dt
=
 o doto
Where d is the density of the solution and d0 is that of the solvent. In dilute
solutions, d  d0 hence:

59
 t  t
= and sp = −1 = −1
 o to o to

t − to
sp =
to
Put your results in tabular from as follows:

t − to sp
c (gm / 100 ml) t (sec.) sp =
to c

plot c as the x-axis and  sp  as y-axis, a straight line is obtained whose
 c 
intercept equals the limiting viscosity number [].
substituting for [] in equation 4 gives the viscosity average molecular
weight. For polyvinyl alcohol, equation 4 becomes:

[] = 2.0  10-4  M0.76

60
Report Form
Molecular Weight of a Polymer from Viscosity Measurements
Name Id. No. :
Lab Section Instructor
Date : / /

The polymer used is

The solvent used is
For this system at room temperature:
K=
=
The time of flow of solvent alone to = sec.

t − to sp
c (gm / 100 ml) t (sec.) sp =
to c

From the plot [] =

……..
[] = M
M = g / mol.

61
62
Questions

- What do we mean by mono-disperse and poly-disperse polymer?

- Why do we express the concentration of polymer in terms of grams
and not in gram moles in this experiment?
- Mention some examples of polymers in nature of organic and
inorganic types.
- What is the difference between the following terms: dimers,
oligomers, and polymers?
- Mention some other techniques used in polymer molecular weight
determination.
- To fight against environmental pollution, types of "biodegradable
polymers" are now produced. What do we mean by this term?
- What do we mean by polywater?

63
Experiment 16: Solubility of oxalic acid as a function of temperature

Objective:
To measure the temperature dependence of the solubility of oxalic
acid

Discussion:
The solubility of salts in water is a topic of great practical and
theoretical importance, and it continues to be an active area of research.
Our understanding of solubility phenomena has a very direct influence on
our everyday lives. Much physiological, environmental, industrial, and
analytical chemistry is based on the solubility properties of salts, and
research in these areas has brought many practical benefits. Here are just
a few examples:
1- Water pollution by toxic metal compounds is always a serious
problem in an industrial society. Control of metal pollution is limited
by our ability to precipitate the metals as insoluble salts without
introducing new chemicals into the water that are equally or more
troublesome.
2- Biologists and biochemists clarify the importance of trace quantities
of certain metals in many physiological processes. One way that
living organisms can adjust the distribution of metals in cells is by
controlling their solubility in body fluids.
3- The good and bad fortunes of human societies are always tied closely
to their ability to grow sufficient food. Present population pressures
make agricultural use of artificial fertilizer essential because high
agricultural productivity would otherwise rapidly deplete the
essential nutrients in the soil. The cycling of minerals nutrients
through the environment in forms useful to plants and animals is
largely governed by water solubility phenomena. Our understanding
of these processes helps us to use the natural cycles more effectively
and to know when and how to give assistance with manufactured
fertilizers.
4- In the areas of industrial and analytical chemistry, literally thousands
of processes are based on the separation of different substances by
their solubility characteristics. There is much current research in all
these areas. The measurement of the temperature dependence of
solubility for a particular substance, as in this experiment, provides
basic information essential to all the above applications.

64
Heat Changes Accompanying the Process of Solution
You probably can recall the first time you prepared sulphuric,
hydrochloric, or nitric acid with water. If you did it carefully and correctly,
you slowly poured the acid into the water with constant stirring, and you
undoubtedly observed that the solution becomes warm, perhaps even
hot. Less noticeable, perhaps but easily observed, is the fact that
dissolving some substances, such as potassium nitrate (KNO 3), in water
cools the solution. In general, when a substance dissolves in a solvent,
heat is either released (heating the solution) or absorbed (cooling the
solution). This heat change reflects energy changes in the system due to
the new attractive intermolecular forces between the solute and solvent.
Dissolving a substance in a solvent may be regarded as a reversible
chemical reaction:
solvent + solute solution
The heat change is called the enthalpy of solution (written  H, and
may be a positive or negative quantity). Enthalpy of solution is considered
negative when heat is released (because the reactants lose energy to the
surroundings), and vice versa.
A completely quantitative discussion of solubility is very
complicated, and it is not possible to lay down any hard and fast rules on
this topic. However, we shall point to a few important factors that are
involved in a comparative treatment.
Consider the process of a simple ionic compound, M+ X-, dissolving
in water which may be represented as
M+X-(s) + Water +
M(aq) + X-(aq) (H)
This process may be broken down into two hypothetical stages as follows:
M+ X-(s) ⎯⎯→ M+(g) + X-(g) (positive lattice enthalpy)
M+(g) + X-(g) + Water ⎯⎯ +
→ M(aq) + X-(aq) (negative lattice enthalpy)
In the first stage the lattice enthalpy is absorbed in separating the
ions and effectively removing them to infinity. In the second stage,
hydration enthalpies of the two ions are released. The enthalpy of
solution is the algebraic sum of these two enthalpy changes. It is likely
that a strongly positive enthalpy of solution will be reflected as a low
solubility. This is achieved when the lattice energy (e.g., in covalent
compounds) is high and the hydration energy is low (e.g., in the case of
solvents other than water).
Le Chatelier’s principle is applied to an equilibrium situation, i.e.,
when solid is in contact with its saturated solution. The dissolving of an
ionic compound in its saturated solution is an endothermic process (H is

65
positive) and solubility decreases with temperature. This is the case for
example, with Li2CO3 whose solubility in water decreases with
temperature. (At 10C, the solubility of Li2CO3 in water is 1.43 g per 100 g
water and at 100C, it is only 0.72 g per 100 g water).
In this experiment, you will measure the solubility of an unknown
substance at different temperatures. From your data, you can make
graphs showing the temperature dependence of solubility and predict the
sign of H, for the unknown. For sodium sulphate, a transition in its
structure occurs at 32C. below this temperature, it occurs as sodium
sulphate decahydrate Na2SO4.10H2O. Above this temperature, it exists in
the anhydrous form; Na2SO4.
The measurement involves dissolving a known amount of solute in
hot water, allowing the solution to cool, and observing the temperature
at which the solution becomes saturated, and precipitation begins.

Procedure:
1- Take 2.1347 g of oxalic acid
2- Add 1 ml distilled water
3- Heat until dissolution
4- Leave to cool and record the temperature at which crystals just start
to form
5- Repeat this step after adding 2 ml, 2 ½ ml, 3 ml, 3½ ml, 4 ml and 4½
ml water to the test tube
6- Tabulate your results as then plot the solubility in g 1 ml again
temperature Show whether the solubility process in endothermic or
exothermic and determine the solubility of oxalic acid at 50 ºC.

Calculations:
……………..………………………..………………………..………………………..……………………
…..………………………..………………..………………………..………………………..……………

Results Weight of oxalic acid = 2.1347 ºC

ml water Solubility g /ml Temp. ºC
1.0
2.0
2.5
3.0
3.5
4.0
4.5

66
67
Experiment 17: Diffusion of ammonia and hydrogen chloride gas-
verification of Graham’s law of diffusion.

Objective:
To verify Grahams law of diffusion

Introduction:

Gas diffusion and effusion

Gas diffusion usually occurs through membranes such that the
pressures on both sides of membrane are the same. On the other hand,
gas effusion occurs through tiny holes under the influence of higher
pressure on one side (Figure 1)

.......
..
........
...........................
............ ......
.........................
P P
.... .
........
. Compressed
Gas (2) Gas (1) gas
Memberane
Effusion
Diffusion

Fig. 1 Difference between diffusion and effusion.

Gas diffusion is governed by Graham’s law of diffusion in which:

D1 d M2
= 2 =
D2 d1 M1
Effusion, on the other hand, is governed by the relation:
t2 M2
=
t1 M1
where t is the time of effusion of a certain volume of the gas.

One of the important applications of gas diffusion is isotope

separation. An example is to enrich uranium i.e., making it rich in the
isotope 235
92 Uwhich is the useful isotope in nuclear fission.

Uranium ore, known as pitchblende, contains 235 and 238 isotopes

in the ratio 0.71% and 99.28% respectively. Only the 235 isotope is useful

68
in nuclear fission. The ore is first transformed to the hexafluoride gaseous
derivative UF6 of molecular weights as follows:
235
92 UF6 M = 349

238
92 UF6 M = 352

On allowing this mixture to diffuse through several suitable

membranes, then:
D235
= 352 = 1.0043
D238 349
This means that the 235-isotope hexafluoride diffuses 1.0043 times
faster than the isotope 238.

Apparatus and materials

• Glass tube
• Beakers, 250 ml, 2
• Rubber bands, 2
• Aqueous ammonia '880'
• Hydrogen chloride (concentrated; Caution)
• Tweezers
• Cotton wool
• Lab stand, boss and clamp
• Beaker of water

Technical notes
The glass tube should be about 1 m long and 5 cm diameter.
The hydrogen chloride and aqueous ammonia should be in bottles with
close-fitting stoppers.

Safety
Eye protection must be worn.

It is recommended that you arrange this demonstration either in a very

well-ventilated area or outdoors.

69
Procedure

a Soak a ball of cotton wool in aqueous ammonia and insert a few

centimeters into the glass tube. Rinse the tweezers in water and
dispose of excess ammonia. Close the end with the rubber bung. At the
same time, insert a cotton wool ball soaked in hydrochloric acid at the
other end. Rinse the tweezers again in water to avoid corrosion.
b Watch carefully. Where the two vapors meet a ring of thick "mist" will
form. The position of the ring will suggest which vapor diffuses more
quickly. (The demonstration takes 15 to 20 minutes).

Teaching notes
1- Emphasize that the particles of each vapor are moving randomly.
2- Through questioning, the students should be able to realize that the
ammonia (molar mass about 17 g) is diffusing more quickly than the
hydrogen chloride (molar mass about 36 g).
3- Further questioning can develop ideas about why the lighter gas
diffuses faster. The mean kinetic energy of each gas particle is the
same if the temperature is the same. Therefore, the more massive
gas will be travelling more slowly and hence diffuse more slowly
(why?). This is borne out by the experimental observations.

70
Experiment 18: The Density of a Single Crystal of Ammonium Oxalate
Monohydrate by the Floatation Method*.

Objective:
To determine the density of a crystal by floatation method

Discussion:
Most introductory chemistry courses include density
determination in the laboratory. The objects which are used are usually
large, can be weighed, and their volumes measured. Of particular interest
to students is the determination of the density of a single crystal which
can neither be weighed nor its volume determined accurately.
The density of a single crystal of ammonium oxalate monohydrate
can be determined rapidly by using a test tube, two burettes, and the
acetone/carbon tetrachloride liquid pair (dry methanol can be used
instead of acetone). A single crystal of (NH4)2 C2O4.H2O floats in pure CCl4
3
, which has a density of 1.59 g/cm . When placed in pure acetone, which
has a density of 0.791 g/cm3, a single crystal of ammonium oxalate
monohydrate sinks. Because of these features, there exists a mixture of
carbon tetrachloride and acetone in which a single crystal of ammonium
oxalate monohydrate neither sinks nor floats but remains suspended in
the liquid pair. The density of this liquid pair will be the same as the
density of the single crystal.

Experimental
Withdraw 5.00 ml of CCl4 from a burette into a large dry test tube.
Place a single crystal of ammonium oxalate monohydrate into the test
tube and begin dropwise addition of acetone from a second burette.
Thoroughly mix the contents of the test tube after each acetone addition;
this is accomplished by vigorous swirling. Acetone should be added until
the crystal becomes suspended in the liquid pair. The density of the liquid
pair, which is numerically equal to the density of the crystal, is calculated
according to

(DCCl4 g/cc )(VCCl4 ml ) + (Daceton g/cc )(Vacetone ml )

DCCl 3 =
4 acetone pair (g/cm ) mlCCl4 + mlacetone

*
T. J. Bergendahl, J. Chem. Educ. 56 (1979) 617.
71
Calculations:
……………..………………………..………………………..………………………..……………………
…..………………………..………………………..…..……………………..………………………..…
……………………..………………………..………………………..………………………..……………
…………....

72
Experiment 19: Chemical synthesis gold nanoparticles
Preparation of gold nanoparticles (Sodium citrate reduction
method) is carried out as follows:
1. Make a solution of 2.5  10-4 M HAuCl4.xH2O in distilled
water. (HAuCl4 is hydrogen tetrachloroaurate. It is supplied
in tri- or tetra-hydrated forms).
2. Take 4 ml of that solution in a clean test tube.
3. Make a solution of 0.2% citrate trisodium salt
(C6H5O7Na3.3H2O; M.Wt. = 312.06 g/mol) (0.2 g in 100 ml of
H2O).
CH2COONa
NaOOC C OH
CH2COONa

4. Heat the 4 ml solution of HAuCl4 with shaking until it begins

to boil.
5. Add 1 ml of 0.2% sodium citrate solution as soon as boiling
commences.
6. Continue heating with shaking until color change is evident
(pale purple).
7. Remove the solution from the heating element and continue
to shake until it has cooled to room temperature.
8. Transfer your gold solution to a 5 ml volumetric flask and
complete to the mark using drops of distilled water to
account for vaporization of water during boiling.

This method is referred to as Turkevich method which yields uniform

size nanoparticles with diameter of 15-20 nm. The citrate anion is
adsorbed on the produced gold nanoparticles surfaces and act as a
stabilizer that prevents their aggregation.
Before the color changes are observed, there is an induction or
waiting period of about 5 minutes, which is due to the formation of a
precursor called acetone dicarboxylic acid, a product of the oxidation of
citrate. The reduction of gold ions occurs through the following steps:

73
 CH 2 COOH CH2COOH
Oxdation
HO C COOH C O + CO + H2O

CH 2 COOH CH2 COOH

4Cl + Au Reduction AuC l 4

o
ESHE :1.002V

In this approach, acetone dicarboxylic acid plays the roles of

precursor, reducing and nucleating agents. The first stage is the oxidation
of citrate into acetone dicarboxylic followed by the reduction of gold ions
into atoms. The acetone dicarboxylic acid molecule has two groups per
unit, which may form a bond with the gold ion. It is well known that this
intermediate can form complexes with metal ions such as copper, iron, or
mercury ions. In fact, the reduction of gold from the oxidation state + III
to + I is not a direct process and an intermediate product is formed before
further reduction. The mechanism of the successive reduction of
tetrachloride gold ions is displayed in Figure 2.
Au -
- Cl Cl
Cl Cl oxidation of citrate -
OO
Au Ac Au
-
Cl Cl n OO -
- Cl
OO
te Ac Au
i tra -
fc OO Cl
o no
id ati
o x
ti on
c lea
Nu

Au Growth

Fig. 2 Mechanism of formation of gold nanoparticles by citrate reduction

The final reaction is given as follows:

Calculation of the concentration of a gold nanoparticles solution

In a typical experiment, approximately 13 nm diameter Au
nanoparticles were prepared by the above citrate reduction method
which resulted in a change in solution color from pale yellow to pink color.
A typical solution of 13 nm diameter gold particles exhibits absorbance at
520 nm.

74
 Given gold crystals having a face-centered cubic (fcc) crystal structure
with cell parameters a = b = c = 4.0782 Å, then calculate the concentration
of the resulting gold nanoparticles solution.
Also calculate the extinction coefficient ε (λ) of the prepared gold
nanoparticles at maximum absorption wavelength of λmax = 520 nm by
measuring the absorbance "A" at λmax = 520 nm.
Procedure:
The fcc unit cell contains four atoms per unit cell.
The corner points: 8×1/8 = 1
The face-centered points: 6×1/2 = 3
Total =4
1 1
Number of atoms per unit cells = 8  + 6  = 4 atoms
8 2
Since eight corner atoms in a cubic system are shared by eight-unit cells
and six face-centered atoms are shared by two unit cells each.

Diameter of gold nanoparticles = 13 nm = 130 Å.

r (radius of Au nanoparticle) = diameter/2 = 65 Å.
Volume of the gold nanoparticles = (4/3) π r3
= (4/3) x 3.14 x (65)3
= 1.15 x 106 ų
Volume of unit cell = a3 = (4.0782 Å)3 = 67.83 ų
67.83 ≡ 4 atoms
1.15 x 106 ≡ X atoms
X = (1.15 x 106 x 4) / 67.827461 = 6.78 x 104 atoms/ nanoparticle.
Each 6.78 x 104 gold atoms are clustered in one nanoparticle.
The total number of gold atoms in the reaction medium is obtained as the
number of HAuCl4 molecules used.
M x V = M' x V'
2.5 x10-4 x 4 = 5 x M'
M' = 2.0 x 10-4
The molarity of gold nanoparticles = 2.0 x 10-4/ 6.78 x 104
= 0.295 x 10-8 M = 2.95 nM

75
Calculation of the extinction coefficient (ε in M-1cm-1)

To calculate extinction coefficient; ε(λ) in M-1cm-1 for the 13 nm diameter

gold nanoparticles:
1- Measure the absorbance at λmax = 520 nm
2- Applying Beer-Lambert law to calculate ε(λ) in M-1cm-1:
ε (λ) = (A/c), ℓ = 1 cm.
Notice the very large extinction coefficient values for nanomaterials
compared with those for ordinary molecules and ions that lie in the range
of 105 M-1cm-1 for totally allowed electronic transitions. This gives
nanomaterials a great advantage in detection techniques.
Compared to the strongly absorbing Rhodamine 6G dye molecules
of strongly allowed electronic transition, (ε = 1.16 × 105 M-1 cm-1
at 530 nm). Thus, gold nanoparticles provide a novel class of photo-
absorber in medical applications.

Gold nanoparticles as nano-sensor

If the citrate anion layer is shielded by adding a strong electrolyte,
such as NaCl, gold nanoparticles will agglomerate (undergo aggregation),
giving rise to change in surface plasmon electronic absorption. For
agglomerated gold, the surface plasmon absorption occurs at about 750
nm causing the solution to turn deep blue as shown in Figure 3.
If high concentration of salt is added, the nanoparticles aggregate
to a point where at which they precipitate, and the solution becomes
clear.
If a weak non-electrolyte is added (e.g., sugar), the electrostatic repulsion
between the gold and the citrate ions is not disrupted and the solution
remains red.

76
 Fig. 3 Non-aggregated (A) and aggregated (B) gold nanoparticles

Procedure

• Prepare a 1 M solution of NaCl by dissolving 0.5 g of NaCl in 10 ml of

distilled water
• Prepare a 1 M solution of sugar by dissolving 2g of sugar in 10 ml of
distilled water.
• Measure 3 ml of nanoparticles and place it in a small vial. Label this vial
as NaCl (ionic compound).
• Measure 3 ml of the nanoparticles and place them in another vial. Label
this vial as sugar (molecular compound)
• Add 5 – 10 drops of the NaCl solution one drop at a time to the vial
marked as NaCl. Record the color changes observed.
• Add 5 – 10 drops of the sugar solution one drop at a time to the vial
marked sugar. Record any color changes observed.
The ionic NaCl solution should cause the gold nanoparticles to
aggregate, and the solution will change from red to blue. The sugar
solution should not show a color change because there are no ions
available to aggregate the charged gold nanoparticles.
Gold nanoparticles in DNA sequence
It is shown that gold nanoparticles of absorption at 520 nm appear
red when suspended in solution. Upon aggregation, their absorption
occurs at ca. 750 nm and they appear blue. This red to blue color change
provides a yes/no answer to the presence of a specific DNA target. This
technology could displace polymerase chain reaction (PCR).
This method was tested for the detection of viral DNA sequence of
the genetic material of hepatitis C virus (HCV) Genotype-4 which prevails
in Egypt. [M. A. Sleim, M. A. El-Harith and E. M. Ebeid, Journal of
Biomedical Nanotechnology, 3 (2007), 360–366].
The method is based on linking mercapto alkyloligonucleotide to
gold nanoparticle probes as shown in Figure 4. A single-strand target

77
oligonucleotide (30 bases) of HCV Genome sequence was introduced into
a solution containing these probes. This resulted in the formation of
polymeric network (See Figure 5) of nanoparticles with a concomitant
red-to-blue color change. The un-optimized system can detect about 10
femtomoles (10-15 mol) of an oligonucleotide.

Fig. 4 Mercapto alkyloligonucleotide-modified 13-nm Au particles and

polynucleotide targets used for examining the selectivity of the
nanoparticle-based colorimetric polynucleotide detection system.
[Selective Colorimetric Detection of Viral DNA Sequence of HCV
Genotype-4 Genetic Material using Gold Nanopaticles, M. A. Sleim, M.
A. El-Harith and E. M. Ebeid, J. Biomed. Nanotechnol. 3 (2007), 360–
366].

Fig. 5 Schematic representation of the concept of generating aggregates

signaling hybridization of nanoparticle-oligonucleotide conjugates with
oligonucleotide target molecules. The number of oligomers per gold
nanoparticle is believed to be much larger than depicted.

78
Exercises
1- Investigating organic redox reactions encountered in gold
nanoparticle synthesis:
One can apply the basic concepts of oxidation numbers to verify the
redox process. The term oxidation is used to include any reaction in which
an atom loses electrons and reduction is a process in which an atom gains
electron.
The concept of oxidation number (or oxidation state) was
introduced to investigate redox reactions bearing in mind the following
rules:
- The oxidation numbers of the atoms in uncombined elements are given
an oxidation number of zero e.g., Mg0 or Cl atoms in Cl2.
- For simple ions, the oxidation number is simply the charge on the ion
e.g. (-1) for Cl- and (+2) for Fe2+.
- For compounds and complex ions, it is necessary to assume that the
electrons in each bond belong to the more electronegative atom.

The overall reaction in gold nanoparticles synthesis by citrate reduction

method is given as follows:
2HAuCl4 + 3C6H8O7 (citric acid) → 2Au + 3C5H6O5 (ketoglutaric acid) + 8HCl
+ 3CO2
The structures of citric and ketoglutaric acids are given as follows:

Citric acid

Ketoglutaric acid
Given the electronegativities of H=2.20, C= 2.55 and O= 3.44, then
for citric acid and taking carbons as the atoms undergoing change in
oxidation number in the above reaction, we have three carboxylate
carbons with oxidation number +3 each. We also have two –CH2- carbons
of oxidation number -2 each. Finally, we have carbon linked to a carboxyl

79
group of an oxidation number +1. Therefore we have a sum of oxidation
numbers for carbons in citric acid as: 3×(+3) + 2×(-2) + 1× (+1) = +6.
Notice that C-C bond electrons do not count to oxidation numbers
because the difference in electronegativities is zero. For ketoglutaric acid
and CO2 as products, and taking carbons from left to right, the oxidation
numbers are respectively: +3, +2, -2, -2 and +3. Therefore, we have a sum
of oxidation numbers for carbons in ketoglutaric acid as +4. Another
carbon in the product belongs to CO2 of oxidation number +4. The total
oxidation numbers of carbons in the reaction products are +8. This means
that two electrons are given out for each citric acid transforming to
ketoglutaric acid and CO2 molecule. For 3 molecules, we have 6 electrons
that are used up to reduce 2 Au3+ ions in HAuCl4 molecules into metallic
Au0.
2- The principal of complementary colors
The color display by gold nanoparticles demonstrates the principal
of complementary colors. Visible light extends from the violet end of the
spectrum which has a wavelength of about 400 nm., to the red end, with
a wavelength of less than 800 nm. White daylight color consists of three
primary colours (red, yellow, and blue), and three secondary colours
(orange, green and violet).
When the three primary colours are mixed, the result is white light.
Each secondary color is the sum of two adjacent primary colors ( e.g.
green = blue + yellow ) and each secondary color has a complementary
color of the primary color opposite to it on the color triangle. Colored
substances contain species that can absorb photons of visible light.
Colorless substances do not absorb in the visible region .
Gold nanoparicles of single absorption peak around 520 nm in the
green region appear red in color since the red and green are
complementary colors.

80
81
 Atomic Weights (referred to 12C = 12.000 amu.)

Atomic Atomic Atomic Atomic

Element Symbol Element Symbol
Number Weight Number Weight
Actinium Ac 89 [227]* Mendelevium Md 101 [258]
Aluminum Al 13 26.98154 Mercury Hg 80 200.59
Americium Am 95 [243] Molybdenum Mo 42 95.94
Antimony Sb 51 121.75 Neodymium Nd 60 144.24
Argon Ar 18 39.948 Neon Ne 10 20.179
Arsenic As 33 74.9216 Neptunium Np 93 237.0482
Astatine At 85 [210] Nickel Ni 28 58.69
Barium Ba 56 137.33 Niobium Nb 41 92.9064
Berklium Bk 97 [247] Nitrogen N 7 14.0067
Beryllium Be 4 9.01218 Nobelium No 102 [259]
Bismuth Bi 83 208.9804 Osmium Os 76 190.2
Boron B 5 10.81 Oxygen O 8 15.9994
Bromine Br 35 79.904 Palladium Pd 46 106.42
Cadmium Cd 48 112.41 Phosphorus P 15 30.97376
Calcium Ca 20 40.08 Platinum Pt 78 195.08
Californium Cf 98 [251] Plutonium Pu 94 [244]
Carbon C 6 12.011 Polonium Po 84 [209]
Cerium Ce 58 140.12 Potassium K 19 39.0983
Cesium Cs 55 132.9054 Praseodymium Pr 59 140.9077
Chlorine Cl 17 35.453 Promethium Pm 61 [145]
Chromium Cr 24 51.996 Protactinium Pa 91 231.0359
Cobalt Co 27 58.9332 Radium Ra 88 226.0254
Copper Cu 29 63.546 Radon Rn 86 [222]
Curium Cm 96 [247] Rhenium Re 75 186.207
Dysprosium Dy 66 162.50 Rhodium Rh 45 102.9055
Einsteinium Es 99 [252] Rubidium Rb 37 85.4678
Erbium Er 68 167.26 Ruthenium Ru 44 101.07
Europium Eu 63 151.96 Samarium Sm 62 150.36
Fermium Fm 100 [257] Scandium Sc 21 44.9559
Fluorine F 9 18.9984 Selenium Se 34 78.96

82
Atomic Weights (referred to 12C = 12.000 a.m.u.) (Continued)

Francium Fr 87 [223] Silicon Si 14 28.0855

Gadolinium Gd 64 157.25 Silver Ag 47 107.868
Gallium Ga 31 69.72 Sodium Na 11 22.98977
Germanium Ge 32 72.59 Strontium Sr 38 87.62
Gold Au 79 196.9665 Sulfur S 16 32.06
Hafnium Hf 72 178.49 Tantalum Ta 73 180.9479
Hahnium Ha 105 [262] Technetium Tc 43 98.9062
Helium He 2 4.00260 Tellurium Te 52 127.60
Holmium Ho 67 164.9304 Terbium Tb 65 158.9254
Hydrogen H 1 1.0079 Thallium Tl 81 204.383
Indium In 49 114.82 Thorium Th 90 232.0381
Iodine I 53 126.9045 Thulium Tm 69 168.9342
Iridium Ir 77 192.22 Tin Sn 50 118.69
Iron Fe 26 55.847 Titanium Ti 22 47.88
Krypton Kr 36 83.80 Tungsten W 74 183.85
Kurchatovium Ku 104 [261] Uranium U 92 238.0289
Lanthanum La 57 138.9055 Vanadium V 23 50.9415
Lawrencium Lr 103 [260] Xenon Xe 54 131.29
Lead Pb 82 207.2 Ytterbium Yb 70 173.04
Lithium Li 3 6.941 Yttrium Y 39 88.9059
Lutetium Lu 71 174.967 Zinc Zn 30 65.38
Magnesium Mg 12 24.305 Zirconium Zr 40 91.22
Manganese Mn 25 54.9380
* Values in brackets are mass numbers of longest-lived or best-known
isotopes

83
Values of Some Fundamental Constants

Value
Quantity Symbol
CGS unit SI unit
Electronic
charge
e 4.802  10-10 esu 1.60219  10-19 C
Planck
constant
h 6.6262  10-27 erg s 6.6262  10-34 J s

Avogadro 6.062295  1023

number
N 6.062295  1023 mol-1
mol-1
Atomic rest 1.6605655  10-27
mass unit
mo 1.6605655  10-24 g
kg
Rydberg 1.0973732  1011
constant
R 1.0973732  109 cm-1
m -1
Bohr radius ao 0.52918  10-8 cm 0.52918  10-10 m
Faraday 9.64935  104 C
constant
F 9.64935  104 C equiv-1
equiv-1
82.056 cm3 atm deg-1 mol-1
Molar gas 8.3144  107 ergs deg-1
constant
R 8.3144 J mol-1 K-1
mol-1
1.98717 cal deg-1 mol-1
k -23 J K-
Boltzmann
0.32993  10-23 cal deg-1 1.38066  10
constant (k = R/N) 1
Velocity of
light
c 2.9979  1010 cm s-1 2.9979  108 m s-1
Acceleration
G 980.665 cm s-2 9.80665 m s-2
of free fall

84
References
1- S. A. Weiner "Introduction to Chemical Principles: A Laboratory
Approach", 6th Edition, Thomson Learning, Inc. London (2005).
2- T. G. Greco, L. H. Rickard and G. S. Weiss "Experiments in General
Chemistry", Pearson Education, Inc. London,(2007)
3- J. M. Wilson , R. J. Newcombe R. J. Denaro, and R. M.W. Rickett
"Experiments in Physical Chemistry", Pergamon Press, Oxford, New
York (1978).
4- R. C. Das and B. Behera, "Experimental Physical Chemistry" Tata
McGraw Hill, New Delhi (1988).

85