UNIVERSITI TUNKU ABDUL RAHMAN

FACULTY OF SCIENCE

KAMPAR CAMPUS

PERAK

BACHELOR OF SCIENCE (HONS) CHEMISTRY

YEAR 1 SEMESTER 1

UDEC 1134
CHEMISTRY LABORATORY I
 UDEC 1134
CHEMISTRY LABORATORY I

No of Title of Experiments Page

experiment No
1 Investigating the properties of Period 3 oxides 1-2
2 Determination of the valency of magnesium 3-4
3 Halogen-halide reactions in aqueous solution 5-6
4 The solubility of some salts of Group II elements 7-8

5 Preparation and reactions of boric acid, H3BO3 9-10

6 Preparation of bis(acetylacetonato)copper(II) 11

7 Synthesis of pentaaminechlorocobalt(III) chloride, 12-13

[Co(NH3)5Cl]Cl2

8 Preparation and studies of potassium tris(oxalato)aluminate(III) 14-16

trihydrate {K3[Al(C2O4)3].3H2O}

9 Preparation and studies of potassium 17-18

diaquabis(oxalato)chromate(III)dihydrate {K[Cr(C2O4)2
(H2O)2].2H2O}

10 Solution - Construction of solubility curve for potassium chlorate 19-20

11 Determination of oxalic acid (HC2O4) and sodium oxalate 21-22
(Na2C2O4)
in a mixture solution

12 Determination of the enthalpy (heat) of reaction of a monobasic 23-24

acid with sodium hydroxide

13 Determination of the molar entropy of fusion of camphor 25-26

14 Experimental applications of Hess’s law 27-29
15 Equilibrium studies 30-33
16 Evaluation of the gas law constant 34-36
17 Reaction kinetics - Determination of the activation energy of 37-38
the reaction between oxalic acid and potassium
permanganate
18 Determination of the activation energy for the reaction of 39-41
bromide and bromate ions in acid solution
19 Kinetics: The rate of a chemical reaction 42-45
20 Kinetic study of reaction between hydrogen iodide and 46-48
hydrogen peroxide by iodometry
21 Kinetics study of the hydrolysis of methyl acetate by acid-base 49-53
titration
22 Cryoscopy: Determination of relative molecular by endpoint 54-55
cryoscopy
EXPERIMENT 1

INVESTIGATING THE PROPERTIES OF PERIOD 3 OXIDES

Objective
To examine the oxides of Period 3 elements and describe their structure and bonding

Introduction

Generally, there are the oxides of metals and non-metals. Structurally, they are covalent
or ionic compounds. You are to do some simple observations and tests, and to find out the
differences between the different types of oxides and to account for these differences.

Materials

 Sodium peroxide
 Magnesium oxide
 Phosphorus (V) oxide
 Silicon (IV) oxide
 Sodium sulphite
 Concentrated sulphuric acid
 Universal indicator

Procedures

(A) Appearance
Examine your oxide samples, and in a larger copy of table 9.1, note for each:
(a) whether it is solid, liquid or gaseous,
(b) its colour (if any)

(B) On mixing with water

1. Set up five test tubes, side by side.
2. Into each test tube pour about 5 mL of distilled water.
3. In the first test tube, place a thermometer.
(a) Note the temperature.
(b) Add half a spatula-tip of sodium peroxide and stir carefully with glass rod.
(c) Note: (i) Record the temperature, (ii) note whether the solid has dissolved and (iii)
anything else you see. For example, is gas evolved at any time?
(d) Note the pH using a universal indicator.
4. Repeat the above step 3(a)-(d), using, in turn, magnesium oxide, silicon (IV) oxide
and phosphorus (V) oxide.

Preparation of SO2 gas

5. Add a little conc sulphuric acid to half a spatula-tip of sodium sulphite in a test tube.
Then quickly bubble the sulphur dioxide through the water in the fifth test tube. Note
the pH indicated using a universal indicator.
1
Results

Table 9.1
Period 3 oxide Sodium Magnesium Silicon (IV) Phosphorus(V) Sulphur
peroxide oxide oxide oxide dioxide
Appearance
Physical state
Colour
On mixing with water
Initial temperature
Final temperature
Does it dissolve?
pH of solution
Other observation(s)
(if any)

Table 9.2
Formula of Oxide
Na2O2 MgO Al2O3 SiO2 P4O10 SO2 Cl2O
Melting point / °C
Boiling point / °C
State at s.t.p.
Action of water
pH of aq. Solution
Acid/base nature
Conductivity of
liquid
Solubility in hexane
Structure
Bonding

Questions

1. Use your experimental results and your text – books (if necessary) to complete a larger
copy of table 9.2.

2. Write equations for any reactions which took place when you added oxides to water.

3. Comment on the change in structure and bonding in the oxides of the elements in the
period between sodium and chlorine.

4. How does the acid – base nature of the oxides of the elements in Period 3 change with
increasing atomic number?

5. Can you relate this change in structure and bonding that takes places along the periods?

2
EXPERIMENT 2

DETERMINATION OF THE VALENCY OF MAGNESIUM

Objective

To study the quantitative relationship between the amount of reactants and products of a
reaction. A known starting mass of magnesium and the measured collection of hydrogen gas will
be used to determine the reaction stoichiometry and the valency of magnesium.

Introduction

Stoichiometry is the study of the quantitative relationship between amounts of reactants

and products of a reaction (that is, how many moles of A react with a given number of moles of
B). In this section, a known starting mass of magnesium and the measured collection of
hydrogen gas will be used to determine the reaction stoichiometry.
Magnesium reacts with hydrochloric acid to form hydrogen gases. The aim of this
experiment is to determine the value of x in the following equation:

X
Mg + X HCI  MgCIX + H2
2

A known amount of magnesium is reacted with a large excess of HCl, and the volume of
H2 evolved is measured. As HCl is in excess, all the magnesium will be consumed, and the yield
of both MgClX and H2 is dependent on the amount of magnesium used. A comparison of the
amount of hydrogen produced with the amount of magnesium consumed will enable the X value
to be determined.

Apparatus and Materials

1. Magnesium ribbon 6. Electrical balance 11. Glass rod

2. HCl (0.5 M) 7. Watch glass 12. Thermometer
3. Burette (50 cm3) 8. Beaker (500 cm3)
4. Pipette (25 cm3) 9. Gauze
5. Retort stand 10. Funnel

Procedure

1. We are going to use the burette upside down to collect the hydrogen, but there is an
unmarked space between the 50 cm3 mark and the tap of unknown volume. Determine
the volume of this unmarked space in a clean, dry 50 cm3 burette by pipetting 25.00 cm3
of water into the vertically clamped burette (right way up). Note the burette reading, drain
the burette and repeat. Leave the water in the burette for 10 min. and check whether leaks
occur.

3
2. Clean a piece of magnesium ribbon with steel wool. Cut off a piece with scissors within
the lengths shown to you. Curl up the ribbon. Tare a watch glass on the four decimal
balance and ACCURATELY weigh between 0.0300 and 0.0360 g of the magnesium
ribbon on the watch glass, which should then be placed inside a 600 cm3 beaker.

3. Take a small filter funnel with a short stem (1.0 - 1.5 cm long) and covered with gauze.
Invert it and place it on the watch glass over the magnesium.

4. Carefully fill the beaker with (tap) water until the level is approximately 0.5 - 1.0 cm
above the end of the funnel stem. Completely fill the burette with 0.5 M HCl, invert it
(with supplied cork pressed flat over the open end) and place it in the water in the beaker,
remove the cork and place the end of the burette over the stem of the funnel, ensuring that
no air enters, and clamp it into position.

5. Remove the excess of water with a pipette until the level is just above the stem of the
funnel.

6. Add about 100 cm3 of 0.5 M HCl to the beaker, using a glass stirring rod to ensure
complete mixing such that the HCl reaches the magnesium. This may be helped by
tapping the watch glass gently with a glass rod.

7. Stir the solution to initiate the reaction and then do not stir further so that the reaction
proceeds unaided. At the completion of the reaction (say 30 minutes) tap the watch glass
gently to dislodge any gas bubbles.

Note: Any magnesium that escapes through the fine gauze will still react with the 0.5 M HCl in
the burette.

Questions

1. It is advisable that the temperature is not taken for at least 20 min. after adding the HCI.
Why is this so?

2. Calculate the moles of hydrogen gas present using the given calculation method.

3. Give the Ideal Gas equation and specify what each variable is. Show one mole of gas at
S.T.P. occupies 22.4 L.

4. What will be the result if hydrogen gas, H2, leaks through the stopcock of the
inverted burette?

4
EXPERIMENT 3

HALOGEN-HALIDE REACTIONS IN AQUEOUS SOLUTION

Objective

To investigate the order of oxidizing ability of the halogen Cl2, Br2, and I2 in aqueous solution.

Introduction

You mix each of the aqueous solutions with halide ion solutions, Cl-(aq), Br-(aq), and I-
(aq) in turn, and see whether a reaction takes place. The addition of hexane to the halogen-halide
mixture enables you to recognize the halogen molecules present. The halogen which oxidizes
most of the other halide ions will clearly be the strongest oxidizing agent.

Materials

Bromine water, Br2 (aq)

Chlorine water, Cl2 (aq)
Iodine solution, I2 {in KI(aq) }
Potassium bromide solution, KBr
Potassium chloride solution, KCl
Potassium iodide solution, KI
Hexane, C6H14

Halogen and organic vapours must not be inhaled. KEEP HEXANE AWAY FROM FLAMES.

Procedure

1. Reaction (if any) of iodide with chlorine and bromine

(a) To each of two test tubes add about 1 mL of potassium iodide solution
(b) To one of these tubes, add about the same volume of chlorine water, and to the
other add the same volume of bromine water.
(c) Shake the tubes and note the colour change – if any.
(d) To each tube add a few drops of hexane, shake and allow to settle, and note the
colour of each layer.
(e) Decide which reactions have taken place, and complete a copy of Result in
Table 11.1.

2. Reaction (if any) of bromide with chlorine and iodine

Repeat the above steps, 1(a) – (e), using potassium bromide with chlorine water and
iodine solution.

3. Reaction (if any) of chlorine with bromine and iodine.

Repeat the above steps, 1(a) – (e), using potassium chloride with bromine water and
iodine solution.

5
Results

Table 11.1

Chlorine Bromine Iodine

water water solution
Initial colour
1. Colour after shaking with KI
solution
Colour of each layer Upper
after shaking with Lower
hexane
Conclusion
2. Colour after shaking with KBr
solution
Colour of each layer Upper
after shaking with Lower
hexane
Conclusion
3. Colour after shaking with KCl
solution
Colour of each layer Upper
after shaking with Lower
hexane
Conclusion

Questions

1. (a) Does I2 ( aq KI) oxidize Cl-(aq) and Br-(aq) ?

(b) Does Br2 (aq) oxidize Cl-(aq) and I-(aq) ?
(c) Does Cl2 (aq) oxidize Br-(aq) and I-(aq) ?

2. Write ionic equations for the reactions taking place.

3. Base on the results of the experiment; arrange the halogen in order of increasing
oxidizing ability.

6
EXPERIMENT 4

THE SOLUBILITY OF SOME SALTS OF GROUP II ELEMENTS

Objective

To demonstrate the trends in solubility of the Group II carbonates, sulphates, sulphites, and
hydroxides.

Introduction

In this experiment, you add each of the anion solutions to 1 mL of each cation solution
provided, drop by drop, until the first sign of a precipitate appears. For each salts, the solubility
is proportional to the number of drops of anion added.

Materials

0.1 M solutions of the following cations : Mg2+, Ca2+, Sr2+, Ba2+,

1.0 M solution of OH-
0.5 M solutions of SO42-, and SO32- ions, 0.05 M solution of CO32-.

Procedure

1. Set up two rows of four test-tubes each.

2. For first row, label the first test tube Mg2+, the second test tube Ca2+, the third test tube
Sr2+, and the forth test tube Ba2+.
3. Add 1 mL of the appropriate cation solution to each test tube, using a teat pipette with a 1
mL mark.
4. Label the second row of test-tubes OH-, the second row SO42-, the third row SO32- and the
fourth row CO32-.
5. Add the OH-, drop by drop, with shaking, to each cation solution in the first row, until the
first sign of precipitate appears.
6. Record the number of drops of solution used in a copy of Result Table 8.1.
7. Repeat Steps 5 and 6 with the remaining anions and cations.
8. If a precipitate appears suddenly, during the addition of a drop, then you should classify
the precipitate as slight (s) or heavy (h).
9. If no precipitate appears after forty drops, then write ‘40+’ and regard the salt as soluble.

7
Results

Table 13.1

Cation Number of drops of anion solution added to

solution give a precipitate
OH- SO42- SO32- CO32-

Mg2+

Ca2+

Sr2+

Ba2+

Table 13.2 Solubilities of Group II compounds in water at 298 K

Singly – charged anions Doubly – charged anions

Solubility / mol per Solubility / mol per
Compound Compound
100g of water 100 g of water
MgCl2 5.6 x 10-1 MgCO3 1.8 x 10-4
CaCl2 5.4 x 10-1 CaCO3 0.13 x 10-4
SrCl2 3.5 x 10-1 SrCO3 0.07 x 10-4
BaCl2 1.5 x 10-1 BaCO3 0.09 x 10-4
Mg(NO3) 4.9 x 10-1 MgSO4 3600 x 10-4
Ca(NO3) 6.2 x 10-1 CaSO4 11 x 10-4
Sr (NO3) 1.6 x 10-1 SrSO4 0.62 x 10-4
Ba(NO3) 0.4 x 10-1 BaSO4 0.009 x 10-4
Mg(OH)2 0.020 x 10-3 MgCrO4 8500 x 10-4
Ca(OH)2 1.5 x 10-3 CaCrO4 870 x 10-4
Sr(OH)2 3.4 x 10-3 SrCrO4 5.9 x 10-4
Ba(OH)2 15 x 10-3 BaCrO4 0.011 x 10-4

Questions

1. For Group II, what are the trends in solubility of the salts listed below:
(a) hydroxides (b) sulphates (c) sulphites (d) carbonates

2. Use Table 13.2 to answer the following questions

(a) Explain the trends in solubility for each type of salt for Group II elements as listed
in Table 13.2.
(b) Do the solubilities give above for the carbonates, sulphates and hydroxides agree
with your findings in this experiment.
(c) So singly- or double-charged anions give the more soluble compounds?
8
EXPERIMENT 5

PREPARATION AND REACTIONS OF BORIC ACID, H3BO3

Objective

To prepare and carry out tests on the prepared sample of boric acid.

Introduction

Boron is an element in p-block of the periodic table. It has the electron configuration
1s22s22p1 and is in Group III (Mendeleev Classification) or in Group 13 (IUPAC classification).
In nature, it consist of two isotopes 10B (19.6 %) and 11B (80.4 %).
Boron in nature is bonded to oxygen. The important sources of boron are borax and
kernite, Na2B4O5(OH)4.nH2O (n = 8 for borax and 2 for kernite).
Boron oxides and their derivatives are technologically important and are relatively
inexpensive to produce. Essentially all boron in Nature is in oxygenated form. Boron-oxygen
compounds contain predominantly trigonal planar BO3, and to a lesser degree tetrahedral BO4
units, as in the borate anions.
The B-O bond is quite strong (560-790 kJ mol-1), and boranes and related compounds are
thermodynamically unstable relative to B2O3 and B(OH)3. The principal oxide, B2O3, is very
difficult to crystallize and normally exists in a glassy state (d=1.83 g cm-1) composed of
randomly orientated B2O3 rings with bridging O atoms. In the normal crystalline form, trigonal
BO3 linked through their oxygen atoms; at high pressures and temperatures a high density
(d=2.56 g cm-3) phase having tetrahedral BO4 being produced. Molten B2O3 (m.p. 450oC) readily
dissolves metal oxides to form coloured borate glasses, and this is one of the main commercial
uses of boric oxide. In particular, borosilicate glasses find wide applications in glassblowing and
the production of glass objects because of their small coefficient of thermal expansion.
Hydrolysis of B2O3 generates orthoboric acid (boric acid), B(OH)3, another major
commercial product that is manufactured on a scale of hundreds of thousands of tons per year by
acidification of aqueous solutions of borax, a naturally occurring mineral.

Procedure

1. Dissolve 10g of sodium tetraborate (borax) in 40 cm3 of water.

2. Boil and add 5cm3 of conc. hydrochloric acid.
3. On cooling, boric acid crystallises out.
4. Filter off the crystals using suction and wash well with ice-cold water.
5. Record the yield.

9
Carry out the following tests on the prepared sample, giving equations where possible.

1. Dissolve a little boric acid in water in a test-tube and add a drop of methyl red indicator.
Repeat this in a second test-tube using mannitol instead of the acid. Mix half of each
solution in a third test-tube and record any colour changes. Explain the results.
2. To a few crystals of boric acid in a test-tube add a little methanol and some conc.
sulphuric acid. Heat and ignite the vapour evolved. Report and explain the colour of the
flame.

Questions

1. Draw the structure of all possible borate anions.

2. Find out the properties and structure of boric acid.

3. How do you convert boric acid to boric oxide?

10
EXPERIMENT 6

PREPARATION OF BIS(ACETYLACETONATO)COPPER(II)

Objective

To synthesize the bis(acetylacetonato)copper(II) complex

Introduction

Complexes consist of a central metal atom surrounded by various other atoms or small
molecules called ligands. It is important to recognize the nature of the ligand – the availability of
coordination sites or ligating atoms and the conditions under which these are available for
coordination.

Procedure

1. Dissolve 6g of copper (II) nitrate (Cu (NO3)2.3H20) in 60 cm3 of water.

2. Slowly add, with stirring, the solution of 1:1 ammonia until the precipitate first formed
has just redissolved.
3. Continuing to stir the solution then add drop wise 6 cm3 of acetyl acetone.
4. Filter off the crude product by using suction filtration.
5. Then wash it well with water, and drain it thoroughly.
6. Calculate the percentage (%) yield.

Questions

1. Draw the structure of the complex.

2. Describe the structure by mentioning the ligating atoms of the ligand and its geometry.

Discuss the synthesis of the complex.

11
EXPERIMENT 7

SYNTHESIS OF CHLOROPENTAAMMINECOBALT(III) CHLORIDE,

[Co(NH3)5Cl]Cl2

Objective

To synthesize the chloropentaamminecobalt(III) chloride complex.

Introduction

Complex compounds comprise of a large group of chemical compounds and is derived

from chemical elements, primarily from metals and in particular transition metals. Coordination
complexes exists in different forms, such as SO42-, MnO4-, [FeCN6]2-, etc.
Many metallic salts exists in the hydrated form, for instance, CoCl2.6H2O and consists of
the complex ion such as [Co(H2O6]2+ here six water molecules act as the ligand bonding directly
to the central metal ion, Co2+, by coordinate bond through the donor atom from the ligand, that
is, the oxygen atom from the H2O ligand.
The ligands are arranged in an ordered manner around the central metal atom. Although
there are a number of stereochemistry’s associated with these complexes but the most common
ones are those of coordination number 4 (with tetrahedral or square planar geometries) and 6
(with geometries that approximate an octahedron).
The objective of this experiment is to synthesize the chloropentaaminecobalt(III) chloride
complex. The scheme of the reactions for the preparation is given below:

2CoCl2.6H2O + 2NH4Cl + 8NH3 +H2O2  2[Co (NH3)5(H2O)] Cl3 + 12H2O

[Co (NH3)5(H2O)]Cl3  [Co (NH3)5Cl]Cl2 + H2O

Materials

Aqueous concentrated ammonia solution

Ammonium chloride
Cobalt(II) chloride 6-hydrate
Hydrogen peroxide solution
Concentrated hydrochloric acid

Procedure

1. In 7.5 mL aqueous concentrated ammonia solution, add 1.25g ammonium chloride.

2. With stirring, add 2.5g cobalt (II) chloride 6-hydrate in small portion. Do not add the next
portion until the added portion has dissolved. A yellow precipitate will form easily.
.
3. To the slurry above, with stirring, add slowly hydrogen peroxide solution (2.0 mL, 30 %
v/v). A strong reaction will occur.

12
4. After the reaction has stopper add slowly 7.5 mL concentrated hydrochloric acid solution
to the red aquapentaammine solution.

5. Heat this product on a hot water bath for 20 min. Filter off the product by vacuum suction
and washing with cold water.

Questions

1. Draw the structure of the complex.

2. Describe the synthesis of the complex.

3. Based on your understanding, why is it that the crystals obtained have to be washed with
cold water?

4. What are the impurities that may be present in the product?

5. Assuming that the reactions go to completion, how many moles of the product are
expected?

6. Calculate the percentage yield of your product.

7. Suggest how the percentage yield can be improved in the experiment above.

References

1. Cotton, F. A. and Wilkinson, G., “Advanced Inorganic Chemistry”, 3rd Ed.’ Wiley-
Interscience (1972).
2. Huheey, J. E., “Inorganic Chemistry”, 2nd Ed., Harpers Row (1978).

13
EXPERIMENT 8

PREPARATION AND STUDIES OF POTASSIUM TRIS(OXALATO)ALUMINATE(III)

TRIHYDRATE {K3[AL(C2O4)3].3H2O}

Objective
To prepare Potassium tris(Oxalato)aluminate(III)trihydrate {K3 [Al(C2O4)3].3H2O} and study its
reactions

Introduction

Aluminum occurs widely in nature as aluminosilicate minerals and as bauxite,

Al2O3.xH2O from which the metal can be produced by electrolysis after dissolving in molten
cryolite, Na3AlF6. The metal is mainly used in aluminum alloys. The organoaluminum
compounds (e.g., Et3Al) are used in the catalysts involved in the polymerisation of ethene.
Group 13 (IIIA) of the Periodic Table includes the elements boron (B), aluminum (Al),
gallium (Ga), indium (In) and thallium (Tl). The electronic configuration is ns2np1 and the group
valency is three. Aluminum (atomic number = 13) is present in the third period and contains
empty 3d orbitals and favours the formation of complexes with six coordination number. It forms
stable octahedral complexes with ligands such as 8-hydroxyquinoline which also known as
2-
“oxine” (C9H7NO) and with the oxalate anion (C2O4 ). In this experiment, you are to prepare an
oxalato-aluminum (III) complex and study its reactions.

Preparation

(1) Dissolve 0.0105 mole Al2(SO4)3.18H2O in 100 ml distilled water. Prepare a solution of
5M NaOH in 20 ml of distilled water and add to the above solution dropwise with
stirring.

(2) Filter the freshly precipitated Al(OH)3 using a vacuum filtration technique and wash the
precipitate a few times using 20 ml of distilled water each time.

(3) Weigh 0.0159 mole oxalic acid dihydrate and 0.0163 mole potassium oxalate
monohydrate and dissolve them in 250 ml distilled water in a 500 ml beaker. Add
Al(OH)3 to the solution and heat the mixture on a steam bath with stirring using a glass
rod to dissolve Al(OH)3 (sometimes a little precipitate may remain).

(4) Evaporate the solution to about 30 ml using a rotary evaporator or a hot plate. Gravity
filter the concentrated solution into a 250 ml beaker.

(5) Add 35 ml of ethanol to the solution dropwise over 10 minutes and cool in ice to
precipitate completely colourless crystals of the product.

14
(6) Vacuum filter the product as in step (2) and wash four times with 10 ml ethanol, dry
completely by vacuum suction.

(7) Keep the dry product for the next experiment.

(8) Weigh the product. Transfer about 0.5 g into a small beaker to carry out the following
tests for the presence of potassium, aluminum and oxalate in the product.

Qualitative Analysis

(1) Test for potassium

Perform the flame-test for potassium in a fume cupboard using a platinum wire. Note the
colour of the flame.

(2) Test for aluminum

Dissolve about 0.2 g of the product in 5 ml water and add 2 ml of dilute sodium
hydroxide solution. Note any precipitate in the solution. Now prepare a fresh solution of
0.2 g of the product in 10 ml dilute HCl, warm the solution and add NaOH solution
dropwise until a precipitate is formed and redissolved in excess NaOH. Shake the
solution after each addition.

(3) Test for oxalate

Dissolve 0.5 g of the product in 20 ml distilled water. Divide the solution into two almost
equal portions. Add 5 ml dilute H2SO4, in one of the solutions. Heat both the solutions
and add in each solution 3-4 drops of dilute solution of KMnO4. Note the colour of the
resulting solutions.

Report

(1) Write an ionic equation for the formation of Al(OH)3 using Al2(SO4)3.18H2O and
NaOH.

(2) The formation of the tris(oxalate)aluminate(III) complex anion is carried out by reacting
Al(OH)3 with the exact number of moles of the oxalate ion and oxalic acid. The number
of moles of each reactant is given in step (3) of the preparation section. Using this
information, balance the equation for the reaction:

Al(OH)3 + (C2O42-) + H2C2O4 => [Al(C2O4)3]3- + H2O

(3) Aluminum is present as a free cation when Al2(SO4)3.18H2O is dissolved in water.

Which ions are present when K3[Al(C2O4)3].3H2O is dissolved in water? The function
of acid used in carrying out test (ii) is to release Al3+ from the complex ion,

15
 [Al(C2O4)3]3-. The [Al3+(H2O)6] ion written in simple form as Al3+ is then identified
as described in test (ii). Write equations for the reaction of the acid with the product and
for the reaction which indicates the presence of aluminum (III) in the product.

(4) Aluminum (III) hydroxide is an amphoteric substance i.e., it reacts both with acids and
alkalis to form the aluminum salt of the acid and AlO2- anion respectively. Write
equations for the reactions of Al(OH)3 with HCl and NaOH to indicate the amphoteric
nature of Al(OH)3.

(5) The oxalate ion is oxidised by the permanganate ion in the acid solution. Follow the
following steps to derive the two half ionic equations for this reaction:

Oxidation of oxalate ion to carbon dioxide

(i) Write C2O42- on the left and CO2 on the right of =>.
(ii) Balance the carbon and oxygen atoms.
(iii) Balance the charge by writing electrons (e-) on the right hand-side.

Why is it called an oxidation reaction?

Reduction of MnO4- to Mn2+ in acid solution
(i) Write MnO4- on the left and Mn2+ on the right of =>.
(ii) Balance oxygen by writing H2O on the right hand-side.
(iii) Balance hydrogen by writing H+ on the left hand-side.
(iv) Balance the charge by writing electrons (e-) on the left hand-side.

Multiply with the appropriate factor to obtain the same number of electrons in each half-
equation. Add the two half-equations to obtain the overall equation for the oxidation-
reduction reaction. Why is it called reduction reaction?

What evidence did you see for this redox reaction in test (iii) to indicate the presence of
oxalate in your product?

(7) Calculate the % yield of the product.

(8) Draw the structure of the oxalatoaluminate anion (read the Introduction Section), taking
oxalate as a bidentate ligand.

16
EXPERIMENT 9

PREPARATION AND STUDIES OF POTASSIUM

DIAQUABIS(OXALATO)CHROMATE(III) DIHYDRATE {K[Cr (C2O4)2 (H2O)2].2H2O}

Objective
To prepare potassium diaquabis(oxalato)chromate(III)dihydrate complexes and study its
reactions

Introduction

Chromium (Cr) is found in group 6 (VIB) of the Periodic Table along with molybdenum
(Mo) and tungsten (W). These metals, therefore, have 6 valence electrons. In the chromium
atom, the 3d-orbital is half-filled with 5 electrons and 6th electron is present in 3s orbital. The
most common ore of chromium is chromite [chrome ironstone/iron (II) chromite, FeCr2O4]
which can be used directly for the manufacture of steel and other chromium compounds. An
alloy of chromium and nickel, nichrome is used for electrical heating elements.
Chromium (III), the most stable oxidation state of chromium, forms a number of
complexes, in which six monodentate ligands surround the cation octahedrally. In the above
compound, two oxalate anions (bidentate ligands) and two water molecules coordinate the
chromium cation to provide oxygen atoms at the corners of the octahedron. Two geometrical
- 2-
isomers exist for the complex ion, [Cr(C2O4)2(H2O)2] , two (C2O4) ions [or two H2O molecules]
can be on the same side of octahedron structure of the complex ion giving the cis isomer or on
the opposite sides giving trans isomer.

Preparation

(1) Using a pestle and mortar, powder 0.0555 mole oxalic acid dihydrate and separately
0.0068 mole K2Cr2O7. Mix the powders thoroughly, regrinding them gently.

(2) Transfer the mixture into a 100 ml beaker. Cover with a small watch glass and gently
heat the beaker on the hot-plate. A vigorous reaction commences with the evolution of
steam and carbon dioxide and with the formation of a dark semi-solid compound.

(3) Remove the beaker from the hot-plate and immediately add 15 ml absolute ethanol. Stir
with a glass rod and transfer the mixture into a small mortar (or stir with a beaker and
glass rod). Continue stirring for further 5 minutes breaking up the product and decant the
ethanol. Add a fresh 15 ml absolute ethanol. Grind the product using a beaker and glass
rod until a crystalline violet powder is obtained.

(4) Filter the crystals by vacuum suction using a sintered glass crucible. Wash the crystals
two times with 5 ml ethanol. Dry in the air by vacuum suction. Weigh the product on a
top loading balance, transfer into a properly labelled vial.

17
(5) Carry out the following tests on the product
Qualitative Analysis

(i) Test for potassium

Perform the flame-test for potassium in a fume cupboard using a platinum wire. Note the
colour of the flame.

(ii) Test for cis and trans isomers

The two isomers are in equilibrium when the solid complex is dissolved in water. The
cis- form is more soluble and exists in high proportion in solution but it is slowly converted into
the trans- form when the solution is evaporated slowly. In the solid state only one isomer can
exist depending on the method of preparation of the complex.

Carry out the following test to determine the nature of the isomer prepared in this
experiment:
Moisten a few crystals of the product placed on a small filter paper resting on a watch
glass, first with a few drops of dilute ammonia solution and then with dilute hydrochloric acid.
Record your observations. With the cis- form, a deep-green solution rapidly forms and spreads
over the filter paper, no solid remains. With the trans- form there is no green colour, but a light-
brown solid forms and remains undissolved. In each case, reaction with dilute HCl restores the
original colour of the isomeric form.

Report

(1) What is the oxidation state of chromium in K2Cr2O7 and in the product? Write two half-
equations for each reaction involved in the preparation of the complex using oxalic acid
dihydrate (H2C2O4.2H2O) and potassium dichromate (K2Cr2O7) and a balanced
equation for the overall reaction.

(2) Calculate the % yield of the product.

(3) Write the chemical equations for the reactions involved in the tests for the detection of
chromium (III) and oxalate ions. Indicate in each case whether it is an acid-base or
oxidation-reduction reaction.

(4) Draw the structures of the two possible geometrical isomers of the complex. What is your
conclusion regarding the nature of the isomer in the test (iv)? When dilute ammonia is
added to the solid complex, one molecule of the ligand H2O is replaced by OH- ion.
Write equations for both the isomers to represent this reaction as well as for the reaction
of the hydroxo product and HCl to restore the original complex.

18
EXPERIMENT 10

SOLUTION ─ CONSTRUCTION OF SOLUBILITY CURVE FOR POTASSIUM

CHLORATE

Objective

To construct the solubility curve for potassium chlorate.

Introduction

A solution is homogeneous mixture of two or more substances where the proportions of

which may vary between certain limits. The following types of mixtures may form:
1. gas in gas,
2. gas in liquid,
3. liquid in liquid, and
4. solid in liquid.

This experiment is performed to obtain a solubility curve for solid potassium chlorate in
water at different temperature.

Apparatus and Materials

Solid potassium chlorate

Distilled water
Thermometer (100°C)
Burette
Boiling tube
Hot plate
Beaker
Ice (if necessary)

Procedures

Weigh accurately 3.00 g of potassium chlorate into a boiling tube. Add in 10.0 cm³ of
water from a burette and put a thermometer into the boiling tube. Put the boiling tube into a
beaker of water. Heat the water and stir the content in the boiling tube gently with a glass rod
until the solid has just dissolved completely.

Remove the boiling tube from the hot water, and allow it to cool in air with constant
stirring. Note the temperature at which crystals start to form in the boiling tube. Repeat the
experiment, and determine the temperature again. The average temperature can be taken as the
temperature at which the solution is just saturated.

19
 Now add 5.0 cm³ more of water from the burette, and determine the temperature as
described above. Repeat the procedure until about 40.0 cm³ of water has been added.
Treatment of data

Plot a graph of concentration of potassium chlorate (g / 100 g water) against temperature.

Explain whether the solubility of potassium chlorate in water is an endothermic or exothermic

process.

20
EXPERIMENT 11

DETERMINATION OF OXALIC ACID AND SODIUM OXALATE IN A MIXTURE

SOLUTION

Objective

To determine the percentage of oxalic acid and sodium oxalate in a mixture.

Introduction

Both oxalic acid and sodium oxalate react with potassium permanganate :

2 KMnO4 + 5 H2C2O4 + 3 H2SO4  K2SO4 + 2 MnSO4 + 8 H2O + 10 CO2

or , ionically

2 MnO4- + 5 C2O42- + 16 H+  2 Mn2+ + 8 H2O + 10 CO2

Both oxalic acid and sodium oxalate contain one oxalate ion in a molecule; so the volume
of potassium permanganate can be separated into the portions reacting with oxalic acid and
sodium oxalate.
Only oxalic acid will react with sodium hydroxide, thus can be determined separately:

H2C2O4 + 2 NaOH  Na2C2O4 + 2 H2O

Apparatus and Materials

Sample consists of oxalic acid and sodium oxalate

0.02 M potassium permanganate
1 M sulphuric acid
0.1 M sodium hydroxide
Phenolphthalein indicator
Thermometer

Procedures

a) Titration 1
Pipette 25cm3 of the sample into a conical flask. Acidify with about 15cm3 of dilute
sulphuric acid. Heat until the flask is too hot to touch (~80oC), and titrate with potassium
permanganate. Repeat the titration twice.

21
b) Titration 2
Pipette 25cm3 of the sample into a conical flask. Add a few drops of phenolphthalein
indicator and titrate with sodium hydroxide until the colour of the solution just turns pink. Repeat
the titration twice.

Collected Data

a) Titration 1
Titration number 1 2 3
(Rough)
Initial volume of
burette (cm3)
Final volume of
burette (cm3)
Total volume of
KMnO4 used (cm3)
Average volume of KMnO4 required for titration = ………………………………cm3

b) Titration 2
Titration number 1 2 3
(Rough)
Initial volume of
burette (cm3)
Final volume of
burette(cm3)
Total volume of
NaOH used (cm3)
Average volume of NaOH required for titration = ………………………………cm3

Calculations
1. From the result in titration 1, calculate the concentration of the solution with respect to
oxalate ions (C2O42-).
2. From the result in titration 2, calculate the concentration of oxalic acid in the mixture.
3. Subtract the total oxalate concentration by the concentration of oxalic acid, and calculate
the percentage weight (wt %) of each oxalate in the mixture.

(H2C2O4 ↔ 2 H+ + C2O42-)
(Na2C2O4 ↔ 2 Na+ + C2O42-)

22
EXPERIMENT 12

DETERMINATION OF THE ENTHALPY (HEAT) OF REACTION OF A MONOBASIC

ACID WITH SODIUM HYDROXIDE

Objectives

1. To understand the enthalpy chemistry.

2. To determine the calorimeter constant.
3. To determine the enthalpy of reaction of acid-base reactions.

Introduction

The change in enthalpy that occurs as a result of a chemical reaction is numerically equal to the
heat of reaction under constant (atmospheric) pressure conditions (∆H = q). The heat of reaction
is conveniently measured adiabatically in a Dewar calorimeter by the rise or fall in temperature
of the products produced by the reaction in solution. The “calorimeter constant” must first be
determined. This is the quantity of heat required to increase the temperature of the calorimeter
and its contents by 1 ◦C. The constant is measured by supplying the calorimeter and contents
with a definite known quantity of heat. This can be done electrically or by adding a known
amount of conc. sulphuric acid.

Apparatus and Materials

Dewar flask, stopwatch, thermometer (5 to + 50 ◦C, graduated in 1/10◦C), 50 cm3 graduated

pipette fitted with a suction bulb, 10 cm3 graduated cylinder, conc. sulphuric acid (specific
gravity 1.84, 98.5 % H2 SO4), conc. nitric acid, 1M sodium hydroxide, 0.1 M hydrochloric acid,
methyl orange indicator.

Experimental Procedure

A Dewar flask makes a suitable calorimeter.

1. Calorimeter constant

Pipette 100 cm3 of water into the Dewar flask. Stir the water slowly and regularly with a
1/10 ◦C thermometer (CAUTION: the thermometer bulb is very fragile). Note the
temperature at intervals of 1 minute over a period of five minutes or so. At the end of this
period introduce into the calorimeter about 2 cm3 of conc. sulphuric acid using a
graduated cylinder. Continue recording the temperature at 1 minute intervals whilst
continuing to stir until the rate of fall of temperature has become constant about 10
minutes). Allow the contents of the calorimeter to cool. Titrate 25 cm3 of the solution
against 1 M sodium hydroxide to determine the molarity of the solution.

2. Enthalpy of reaction

23
i) Mix in the calorimeter of known constant 50 cm3 of 1M sodium hydroxide and 50
cm3 of water. Make temperature observations as already described. At a known
time, add 5 cm3 of 10 M nitric acid from a graduated pipette. (Prepare 10 M acid
by diluting 65 cm3 conc. nitric acid to 100 cm3 with distilled water). Continue the
temperature observations. Add to the solution in the calorimeter a few drops of
methyl orange indicator to ensure that the solution is acid. If the solution is
alkaline titrate it in the calorimeter with 0.1 M hydrochloric acid to determine the
exact amount of alkali neutralized during the experiment.

ii) Repeat the experiment described in (i) above but substitute 100 cm3 of distilled
water for the (50 cm3 1M sodium hydroxide + 50 cm3 water) mixture.

Results and Calculations

1. Calorimeter constant

Plot the temperature readings against time and determine the rise in temperature,
∆T, due to addition of acid, as shown in the following diagram.

Project backward to the time of mixing the linear portion CD of the temperature-
time curve to obtain the correct value for ∆T.

The following table give the heat liberated when various quantities or conc.
sulphuric acid are added to 100 cm3 of water.

Acid added Molarity of solution Heat liberated

/ cm3 /M / kJ
0.6 0.108 0.802
0.75 0.138 1.016
1.5 0.276 1.987
2.3 0.421 3.016
2.5 0.459 3.293

24
 Plot a graph of heat liberated against molarity of solution. Read off the heat
liberated (Q) for a solution of the molarity found by titration against 1M sodium
hydroxide previously.
EXPERIMENT 13

DETERMINATION OF THE MOLAR ENTROPY OF FUSION OF CAMPHOR

Objectives

1. To study the molar entropy of fusion of camphor

2. To determine the molar entropy of fusion (Δ Sf) of camphor

Introduction

The molar entropy of fusion (Δ Sf) of camphor may be determined CRYOSCOPICALLY. For
dilute solutions of naphthalene in camphor

Δ T = Kf X

where Δ T = depression of freezing point of the mixture in K

Kf = cryoscopic constant

and X = mole fraction of naphthalene in the mixture

The limit of Kf as X approaches zero i.e.

Lim K f RT02
=
X0  Hf

where R (the gas constant) = 8.314 JK-1mol-1

T0 is the freezing point of pure camphor in K and Δ Hf is the molar enthalpy of fusion of
camphor in J.

 Hf
Since Sf 
T0

Lim K f RT0
thus =
X0  Hf

Apparatus and Materials

On the test tube, 250 cm3 beaker, bunsen burner, 0 – 200 ºC thermometer, tripod and gauge,
retort stand, clamp and boss head, camphor (M = 152 g/mol) and naphthalene (M = 128g/mol).

25
Experimental Procedure

Melt and stir 2 g of camphor in a test tube, then clamp in an air jacket (a large beaker) and allow
it to solidify. Remove the air jacket and heat the test tube gently until melting commences. Stir
the contents with the thermometer and note the temperature at which the last crystal just
disappears. This is the freezing point of camphor. Add 0.05 g of naphthalene to this test tube and
repeat the process. Repeat the procedure for further 0.05 g additions of naphthalene up to a total
weight of 0.20 g of naphthalene.

Results and Calculations

Wt. of No. of Wt. of No. of Freezing

Naphthalene moles of camphor moles of X point (K) ΔT
(g) naphthalene (g) camphor

Plot the value of Kf versus X and extrapolate the graph to X = 0 to obtain

Lim K f
and hence Δ Sf .
X 0

26
EXPERIMENT 14

EXPERIMENTAL APPLICATIONS OF HESS’S LAW

Objectives

1. To determine the enthalpy change of reaction, H by Hess’s law.

2. To study the relationship between change in temperature T and enthalpy change H.

Introduction

An exothermic reaction releases heat into the surroundings and is usually observed as
temperature increases in the solvent, container, and other immediate surroundings. The amount
of heat released from the reaction can be expressed as

qreaction = qsolution + qcalorimeter ……..(1)

In this experiment, the calorimeter is assumed to absorb so little heat that q calorimeter is nearly zero
and thus the equation simplifies to

qreaction = qsolution ……...(2)

The temperature change caused by the addition of a given amount of heat will depend on the
specific heat, Csp of the substance. Thus, the heat involved can be calculated by the equation

Q = (Csp)(m)(T) ………(3)

The mass of the substance is m, and the change in temperature is T (final temperature – initial
temperature)

Since this experiment is run at constant pressure, thus the heat changes observed will be equal to
the enthalpies of reaction, H for the reactions considered. The enthalpies of these directly
observed reactions and Hess’s law will be used to calculate the enthalpy change for an additional
reaction which is not directly observed. Recall that since enthalpy is a state function, the
enthalpy change for any process will depend only on the initial and final states, not on the
reaction path followed. The enthalpy, H(A-B), for the reaction

A  B

can be calculated by adding up the enthalpy changes for a series of intermediate steps.

A  C  D  B

27
Thus, H(A-B) = H(A-C) + H(C-D) + H(D-B). This concept is especially useful in
calculating the enthalpy change for reactions which are not easy to observe or measure directly.

Apparatus and Materials

Dewar flask, thermometer (0-200 C), 50 ml beaker, spatula 2.00 M NH3(aq), 2.00 M HCl(aq),
solid NH4Cl.

Experimental Procedure

Part 1: The reaction of hydrochloric acid solution and ammonia aqueous solution

Measure 25.0 ml of 2.00 M NH3(aq) using a graduated cylinder into a 50 ml beaker. Then
measure 25.0 ml of 2.00 M HCl(aq) directly into Dewar flask. Both solutions should be at or
near room temperature. Record the temperature of each solution. Add the NH3(aq) to the HCl(aq)
in the calorimeter. Stir the mixture slowly and continuously with thermometer and record the
maximum temperature reached by the mixture. Repeat twice.

Part 2: The dissolving of solid ammonium chloride in water

Place 25.0 ml of distilled water into the Dewar flask. Stir carefully with a thermometer until a
constant temperature is reached. Record this temperature. Weigh about 5 g of solid NH 4Cl and
grind thoroughly for 1-2 minutes. Weigh again the sample. Using a spatula, place the solid
NH4Cl into the water in the calorimeter. Stir gently with thermometer until the solid is
completely dissolved and record the maximum temperature reached. Repeat twice.

Results and Discussion

Use Hess’s law to calculate H for the reaction

NH4Cl(s)  NH3(g) + HCl(g)

Given that

H = -34640 J/mole for NH3(g)  NH3(aq)

H = -75140 J/mole for HCl(g)  HCl(aq)

Note that for the purpose of these calculations, we will assume that the densities of all aqueous
solutions are 1.00 g/ml and that their specific heats are equal to 4.184 J/g C.

Questions

Determine the effect that each of the following mistakes would have on
a) The results of the individual sections of the experiment and
b) The final calculated value for the enthalpy of ammonium chloride.

28
In each case state whether the value with the mistake would be greater than, the same as, or
smaller than the value calculated if the mistake had not been made.

Explain your answers.

(i) A student mis-reads the final temperature of the mixture in Part 1, recording a
temperature that is too low.

(ii) A student mis-uses 75.0 ml of each of the solutions in every part of the experiment. The
student, however, records 75.0 ml for each volume and uses this value in his calculations.

29
EXPERIMENT 15

EQUILIBRIUM STUDIES

Objectives

1. To study the effect of concentration and temperature changes on equilibrium

2. To predict the direction of the net reaction in an equilibrium system by Le Chatelier’s
principle.

Introduction

Chemical equilibrium represents a balance between forward and reverse reactions. Changes in
experimental conditions such as concentration, pressure, volume, and temperature disturb the
balance and shift the equilibrium position so that more or less of the desired product is formed.

The outcomes of these changes can be predicted by Le Chatelier’s principle. It states that if a
change is imposed on a system at equilibrium, the position of the equilibrium will shift in a
direction that tends to reduce the effect of the change. For example,

2NO2 (g)  N2O4 (g) H = +57 kJ

In the above reaction at equilibrium, if the pressure is increased (i.e., the volume decreased) the
system will respond to reduce the pressure by shifting to right. Note that there are 2 moles of gas
on the left side of the equilibrium and only 1 mole of gas on the right side. If the mixture is
heated, since it is an endothermic reaction, the system will shift to right to consume the added
energy.

Apparatus and Materials

Test tubes, thermometer (0 – 200 C), solid copper(II) nitrate, 0.4 M cobalt(II) chloride, 0.1 M
potassium chromate, 0.1 M potassium dichromate, 0.2 M HCl, 0.2 M NaOH, thymolphthalein
indicator, 0.1 M ammonia solution, solid ammonium chloride, phenolphthalein indicator

Experimental Procedure

1) Effect of temperature changes on equilibrium

a) Investigate the equilibrium between a solution and a solid.

Cu(NO3)2 (aq)  Cu(NO3)2 (s)

30
 i) Pour some solid copper(II) nitrate into a test tube and fill the tube 1/2 full of
distilled water. Cork and shake to form a saturated solution. If all the Cu(NO3)2
dissolves, pour some additional Cu(NO3)2 in the test tube and shake until a
saturated solution with some excess solid is obtained.
ii) Note the colour of the solution at room temperature. Use a waterproof pen to
mark the level of the top of the solid.

iii) Place the test tube in a beaker of hot water at 60 C. Observe over 30 minutes.
What happens to the level of the solid copper (II) nitrate and the colour of the
solution? Record and explain your observations.

iv) Then place the test tube in an ice bath for another 30 minutes. What happens to
the level of the solid copper (II) nitrate and the colour of the solution? Record and
explain your observations.

b) Investigate the aqueous equilibrium of a cobalt complex.

[Co(H2O)6]2+ (aq) + 4Cl- (aq)  [CoCl4]2- (aq) + 6H2O (l) H = +50kJ/mol

pink blue

(Note: You must retain the cobalt (II) chloride solution at the end of your work on it, and
pass it on to the next student.)

The cobalt (II) chloride solution (0.4 M) will be supplied in a sealed test tube. Sufficient
conc. hydrochloric acid has been added to just turn the colour of the solution mauve.

i) Place the test tube in the 60 C water bath for 15 min, and then examine it for any
change in colour compared to that at room temperature, and record your
observation.

ii) Place the same test tube in an ice bath (or ice/salt) for 15 min and again examine
it for change in colour, compared to that at room temperature, and record your
observation.

iii) By applying Le Chatelier’s Principle, explain the colour changes upon heating
and cooling the cobalt solution and predict what will happen to the equilibrium
system if you add water.

2) Effect of concentration changes on equilibrium

a) Dichromate/chromate equilibrium
The aqueous equilibrium between the chromate ion, CrO42- and the dichromate ion,
Cr2O72- is given as follows:

2CrO42- (aq) + 2H+ (aq)  Cr2O72- (aq) + H2O (l)

yellow orange

31
 i) Place about 5 drops of 0.1 M potassium chromate solution into two small test
tubes and note the colour of the solutions. Label these tubes 1 and 2.

ii) Place about 5 drops of 0.1 M potassium dichromate solution into another small
tube and note the colour. Label this tube 3. (Tube 2 and 3 will be used as a
comparison with the colour in tube 1.)
iii) To tube 1 add 0.2 M HCl dropwise, shaking between additions, until a colour
change is noted. Compare the colour with tube 2 and 3 and record your
observations.

iv) A new state of equilibrium now exists in tube 1. Now add 0.2 M NaOH dropwise
to tube 1, shaking between additions, until a colour change occurs and record your
observations and explanation.

v) Add some more acid by drops to tube 1. Record and explain your observations.

b) Thymolphthalein equilibrium

Acid-base indicators are large organic molecules that can gain and lose hydrogen ions to
form substances that have different colours. The reaction of the indicator thymolphthalein
can be illustrated as follows:

Hln (aq)  H+ (aq) + ln- (aq)

colourless blue

i) Using the supplied thymolphthalein solution and the paint brush, place a small
quantity of the blue solution on a piece of cloth and leave exposed to the air. The
aqueous thymolphthalein solution supplied has been adjusted to about pH 10
using very dilute sodium hydroxide solution.

ii) Notice the change in colour of the blue stain on the cloth. Record the time it took
to change the colour. Obviously the pH of the stain on the cloth is dropping.
However, you have not added any acid. What is present in the air that lowers the
pH? Explain your observations.

c) Ammonium ion / ammonium equilibrium

The equilibrium in a solution of ammonia between the ammonia molecule and the
ammonium ion is as follows:

NH3 (aq) + H2O (l)  NH4+ (aq) + OH- (aq)

i) Working in the fume cupboard, place about 5 cm3 of 0.1 M ammonia solution in
each of two test tubes. Add 2 drops of phenolphthalein to each test tube.

32
 ii) To one of the test tubes add solid ammonium chloride, a little at a time. Shake to
dissolve the solid.

iii) Compare the colour of the test tube with ammonium chloride to that without
ammonium chloride. Record your observations and explanation.

Results and Discussion

Describe the results of each part of the experiment and interpret them using Le Chatelier’s
Principle.

Questions

1) Write down the equilibrium constant expression for the following reaction:

[Co(H2O)6]2+ (aq) + 4Cl- (aq)  [CoCl4]2- (aq) + 6H2O (l)

In which direction will the equilibrium shift if you (a) increase the concentration of
[Co(H2O)6]2+ and b) decrease the concentration of [CoCl4]2-?

2) Using Le Chatelier’s principle, predict the direction of the net reaction in each of the
following equilibrium systems, as a result of increasing the pressure at constant
temperature.

a) N2 (g) + O2 (g)  2NO (g)

b) PCl5 (g)  PCl3 (g) + Cl2 (g)

c) CO (g) + Cl2 (g)  COCl2 (g)

3) What effect (shift to the right or left) does an increase in temperature have on each of the
following systems at equilibrium?

a) 3O2 (g)  2O3 (g) H = 284 kJ

b) 2SO2 (g) + O2 (g)  2SO3 (g) H = -198.2 kJ

33
EXPERIMENT 16

EVALUATION OF THE GAS LAW CONSTANT

Objectives

1. To study the gas law.

2. To determine the gas law constant, R experimentally.

Introduction

This experiment is based on the chemical reaction between magnesium metal 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 used and the
stoichiometry of reaction the number of moles of hydrogen produced can be calculated.

Mg(s) + 2 HCl(aq)  MgCl2(aq) + H2(g)

Since the hydrogen is collected in a eudiometer tube over an aqueous solution, the gas pressure
in the tube after the reaction has ceased is the sum of the hydrogen gas pressure and the vapour
pressure of water. Thus the pressure of the hydrogen is given by

PH2  Patm  PH2O (1)

where Patm and PH 2O are the atmospheric pressure and vapour pressure of water, respectively.

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 tube (hydrogen and water
vapour) will then not be equal to the atmospheric pressure. This difference must then be
subtracted from the atmospheric pressure. Thus, if the levels cannot be equalized, the pressure of
hydrogen must be obtained from the following expression.

PH2  Patm  PH 2O - Plevel difference (2)

where Plevel difference = difference in heights in mm as measured /13.5

Apparatus and Materials

Barometer, Eudiometer tube, copper wire, meter stick, 250 ml beaker, Mg ribbon, concentrated
HCl.

34
Experimental Procedure

1) Calculate the mass of magnesium necessary to evolve 80 ml of H2 at STP. Then weigh

approximately this quantity of Mg ribbon.
2) In the fume hood add approximately 8 ml of concentrated HCl to a eudiometer tube. With
your wash bottle, wash down into the tube any acid that might have adhered to the
eudiometer walls. Coil the weighed strip of Mg ribbon into the eudiometer tube,
approximately 5 to 10 cm from the open end (Copper wire wrapped around the ribbon helps
to keep it in place). Fill the tube with water and invert into a 250 ml beaker nearly filled with
water. The eudiometer volume should read zero if the tube is filled completely with water.
Record the initial reading. Clamp the tube in position as Figure 10.1.

3) The concentration HCl will gradually diffuse down to the Mg and react with it. The Mg may
break free from the copper wire. Tilt the tube to ensure that the Mg does not stick to the sides
of the tube. After reaction has ceased and the difference in levels is large, it must be
measured as shown in Figure 10.1. Note that the graduations on the tube are in milliliters, not
millimeters. You must use a meter stick.

4) Record the temperature of the water in the beaker at 1 min intervals for 5 min. Take the
average value as your gas temperature.

5) Repeat the experiment for a total of three times.

Calculations

1) Calculate the number of moles of magnesium used.

Number of moles of Mg = mass of Mg

24.31 g/mol

2) Calculate the corrected pressure for the experiment as described above using the observed
barometric pressure for the day.

Vapour pressure of water at various temperatures

T / C P / mmHg T / C P / mmHg T / C P / mmHg T / C P / 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

35
3) Calculate R from the equation R = PV/nT

4) Calculate the average value of R.

5) From the theoretical value and your average value for R, calculate the percentage of error in
R.

Figure 10.1 Collecting a gas with the use of an Eudiometer tube

Questions

1) What would be the effect (increase, decrease, or no change) on the calculated value of R of
each of the following experimental errors? Explain each answer.

a) The balance used to weigh the magnesium gives a mass that is higher that actual.
b) Some H2 escapes into the beaker during the reaction.
c) The liquid level in the eudiometer tube is lower than that in the beaker, but this is not
taken into consideration in the calculation.

2) What two safety precautions should you take when using concentrated HCl?

36
3) If 0.071 g of magnesium is used in this experiment, what volume of dry H2 gas would
theoretically be produced if it is measured at 20 C and 785 mm Hg?

EXPERIMENT 17

REACTION KINETICS - DETERMINATION OF THE ACTIVATION ENERGY OF

THE REACTION BETWEEN OXALIC ACID AND POTASSIUM PERMANGANATE

Objective

To determine the activation energy of the reaction between oxalic acid and potassium
permanganate.

Introduction

Reaction between oppositely charged ions are often very fast but the reaction between
similarly charged ions, e.g. permanganate and oxalate, may proceed at a rate which is
measurable :

2KMnO4 + 5H2C2O4 + 3H2SO4  K2SO4 + 2MnSO4 + 8H2O + 10CO2

or

2MnO4‾ + 16H+ + 5C2O42‾  2Mn2+ + 8H2O + 10CO2

The rate of this reaction is measured by the time taken for the disappearance of the purple
colour of the potassium permanganate.

Apparatus and Materials

0.02 M Potassium permanganate

1 M Sulphuric acid
0.5 M Oxalic acid
Test tube
Water bath
Measuring cylinder
Stopwatch
Thermometer

Procedure

Measure 2 cm³ of 0.02 M potassium permanganate and 4 cm³ of 1 M sulphuric acid into a
test tube. In another test tube, place 2 cm³ of oxalic acid. Place the test tubes in a water bath at
35 °C. When the solutions have attained this temperature, pour the oxalic acid into the acidified
permanganate solution and immediately start the time. Record the time taken for the
permanganate to decolorize.

37
 Repeat the experiment at higher temperatures of 40, 45, 50, 55 and 60°C.

Collected data

Tabulate as follows
Temperature, T ( K )
1 / T ( K-1 )
Reaction time, t ( sec )
ln 1/t
Plot a graph of ln 1/ t against 1 / T and calculate the activation energy Ea in J mol –1 according to
the Arrhenius equation
-Ea / RT
k = A e

38
EXPERIMENT 18

DETERMINATION OF THE ACTIVATION ENERGY FOR THE REACTION OF

BROMIDE AND BROMATE IONS IN ACID SOLUTION

Objectives

1. To understand the chemistry of activation energy.

2. To determine the activation energy for the reaction of bromide and bromate ions in acid
solution.

Introduction

The variation of the rate constant, k, of a reaction with temperature, T, can usually be expressed
by the Arrhenius equation
k  Ae-EA/RT
where A is a constant, EA is the energy of activation of the reaction and R is the gas constant.

Taking logarithms of both sides gives

EA
log 10 k  log 10 A -
2.303RT

EA
   constant
2.303RT

Now the time taken (t) to complete a fixed amount of reaction is inversely proportional to k,

1
t 
k

constant
or t 
k

Taking logarithms of both sides,

log10 t  - log10k  constant

39
 EA
  constant
2.303RT
Thus if t is measured at several temperatures the energy of activation may be found.

In this experiment, the above method is applied to the reaction

KBrO3 + 5 KBr + 3 H2 SO4 3 K2 SO4 + 3Br2 + 3H2 O

or BrO3- + 5 Br - + 6 H+ 3 Br2 + 3H2 O

which occurs slowly at room temperature. The time required for a fixed amount of the reaction
be completed (t) is found by adding a fixed amount of phenol and some methyl red indicator to
the reaction mixture. Bromine reacts very rapidly with the phenol (forming tribromophenol).

C6 H5 OH + 3 Br2 C6 H2 Br3 OH + 3 HBr

and when all the phenol has reacted, bromine continuously produced in the first reaction
bleaches the indicator

methyl red + Br2 colourless compound

Apparatus and Materials

1 dm3 beaker, 3 100-cm3 beakers, 2 boiling tubes, 1 5-cm3 pipette, 1 10-cm3 pipette, thermometer
(0 - 110 ◦C), stopwatch, 0.01 mole dm-3 aqueous phenol solution, bromide/bromate solution
(0.0833 mole dm-3 potassium bromide and 0.0167 mole dm-3 potassium bromate, equivalent to
0.05 mole dm-3 bromine). 0.3 mole dm-3 sulphuric acid, methyl red indicator.

Experimental Procedure

Pipette into one of the boiling tubes 10 cm3 of the phenol solution (CAUTION: PHENOL IS
VERY TOXIC) and 10 cm3 of the bromide/bromate solution, and add 4 drops of methyl red
indicator. Pipette 5 cm3 of the sulphuric acid into the other boiling tube. Heat water in the 1 dm3
beaker to a temperature of (75 ± 1) ◦C and adjust the heating to maintain this temperature.
Immerse the two boiling tubes in the water and when they have reached the temperature of the
water, mix the contents of the two tubes by pouring rapidly from one tube to the other twice. At
the same time start the stopwatch. Keep the boiling tube containing the reaction mixture
immersed in the water. Determine the time required for the red colour to disappear.

Repeat the whole experiment at 65, 55, 45, 35, 25 and 15 ◦C, adding ice to the water if necessary
to achieve the lowest temperature (The time t range from a few seconds at high temperatures to a
few minutes at 15 ◦C).

40
Treatment of Results

Plot a graph of the logarithm of the time of disappearance of the red colour (t) against the
reciprocal of the absolute temperature and calculate the slope of the best straight line drawn
through the points.

Results and Calculations

Results should be reported in the form of a table with the following heading:

T(◦C) T(◦K) 1/T(K-1) t(sec)

Finally calculate the energy of activation of the reaction (assume R = 8.314 J K-1 mol -1).

EA
Slope of graph = = k
2.303 R

Energy of activation, EA = ___________ J mol -1

Questions

1. Why is the indicator added in this experiment?

2. Why is the phenol solution added in this experiment?

3. By how much approximately does the reaction rate alter for 10◦ C rise in temperature?

4. How much of the reaction between bromide and bromate ions is completed after time t?

5. If the energy of activation is doubled, would the rate of reaction be expected to increase,
decrease or remain unaffected?
Explain your answer.

41
EXPERIMENT 19

KINETICS: THE RATE OF A CHEMICAL REACTION

(This experiment need 2 practical session)

Note: Two laboratory periods have been allowed for this assignment.

Objectives

1. To study the kinetics of chemical reaction.

2. To study the effects of reactant concentration and temperature on the rate of chemical
reactions.

Introduction

The purposes of this assignment are to study the rate of a chemical reaction, seeing how the rate
varies with reactant concentrations and with temperature, and to see how this data can give
information about the pathway, or mechanism, by which a reaction takes place.

Iodide ions react with persulphate ions to yield iodine.

2 I- + S2 O82- I2 + 2 SO42- …… (1)

Initially the iodine reacts with a small quantity of thiosulphate ions (the same in all experiments)
forming the tetrathionate ion.

I2 + 2 S2 O32- 2 I- + S4 O62- …… (2)

When all the thiosulphate has reacted any further iodine produced turns the solution blue by
complexing with added starch.

We measure the time taken from the mixing of the reactants to the appearance of the blue colour
i.e. the time taken for the formation of a constant amount of I2 by reaction (1).

In part C, the effect of temperature on the rate of reaction will be studied. With the same set of
concentrations, the reaction will be carried out at several temperatures in addition to room
temperature. From these results and equation (3), the activation energy, EA, for the reaction may
be determined.

EA
log10 k    constant … …… (3)
2.303 RT

42
In equation (3), k is the rate constant at each of the different temperatures, EA is the activation
energy in Jmol-1, R is the gas law constant, 8.31415 J mol-1 K-1, and T is the absolute
temperature, K.

Apparatus and Materials

Burettes, 100 and 250 cm3 beakers, stopwatch, thermometer (0 – 110 oC), 100 cm3 graduated
cylinder, 0.2 % starch, 0.01 mol dm-3 sodium thiosulpnate (Na2 S2 O3), 0.2 mol dm-3 potassium
iodide (KI), 0.2 mol dm-3 ammonium persulphate ([NH4]2 S2 O8), 0.2 mol dm-3 potassium nitrate
(KNO3), 0.2 mol dm-3 ammonium sulphate ([NH4]2 SO4).

Experimental Procedures

First practical session

A. The Effect of Varying [S2 O82-]

i) Mix 25 cm3 of the iodide solution, 5 cm3 of the starch solution and 10 cm3 of the
thiosulphate solution in a beaker. Rapidly add 25 cm3 of 0.2 mol dm-3 persulphate
solution, stir and record in the table the time taken from mixing until the blue colour
appears.

ii) Dilute the 0.2 mol dm-3 persulphate solution by mixing 25 cm3 of it with 75 cm3 of the 0.2
mol dm-3 ammonium sulphate solution. Repeat the above experiment using 25 cm3 of this
solution in place of the undiluted persulphate solution.

Note: The 100 cm3 solution must be shared by 4 groups of students to minimize wastage. The
same applies to the solution prepared in part B (ii).

iii) Repeat the experiment at other persulphate concentrations intermediate between the
above two. Again use the ammonium sulphate solution to dilute the persulphate solution.

B. The Effect of Varying [I-]

i) Experiment A (i) will be used for the calculation for maximum iodide concentration.

ii) Dilute the 0.2 mol dm-3 iodide solution by mixing 25 cm3 of the 0.2 mol dm-3 potassium
nitrate. Mix 25 cm3 of this dilute iodide solution, 5 cm3 of the starch solution and 10 cm3
of the thiosulphate solution in a beaker. Rapidly add 25 cm3 of 0.2 mol dm-3 persulphate
solution stir and record the time for the blue colour to appear.

iii) Repeat the experiment at other iodide concentrations intermediate between the above
two. Again use the potassium nitrate solution to dilute the iodide solution.

43
Second practical session

C. The Effect of Temperature

Choosing one of the concentrations from above that you think suitable instead of mixing at room
temperature, warm the mixture of iodide, starch and thiosulphate solutions to about 308 K in a
beaker, then quickly add 25 cm3 of the persulphate solution (still at room temperature) and
record the time of the blue colour to appear and the maximum temperature of the reaction
mixture.

Repeat at an initial temperature of about 288 K and 318 K.

Time (sec)
Temperature (K)

What is the effect of temperature on the rate of the reaction?

Calculations and Questions

a) Is reaction (2) fast or slow with respect to reaction (1)? Explain your reasoning or record any
test you do to help reach your conclusion.

b) Does reaction (1) or (2) control the time required for the blue colour to appear?

d) Calculate the rate of formation of I2 in mol dm-3 s-1 for each experiment at room temperature
and plot this rate

i) against [S2 O82-] at constant [I-]

ii) against [I-] at constant [S2 O82-]

44
Tabulate of Results

[I-] [S2 O82-] [S2 O32-] initial Time Rate of I2 formation

/ mol dm-3 / mol dm-3 / mol dm-3 /s / mol dm-3 s-1

d) What are the shapes of these plots?

e) What is the significance of this?

f) Write the rate equation for reaction (1)

d[I2]
= kx
dt

and calculate the rate constant, k.

g) Calculate the energy of activation of the reaction.

45
EXPERIMENT 20

KINETICS STUDY OF THE REACTION BETWEEN HYDROGEN IODIDE AND

HYDROGEN PEROXIDE BY IODOMETRY.

Introduction

The overall order of the hydrogen iodide - hydrogen peroxide reaction was reported to be 2, not
3,

2 HI + H2O2 I2 + 2 H2 O (in acid solution)

And the observed rate equation is given by

- d [H2O2 ] = k 2 [HI] [H2O2 ]

dt

where k 2 is the second order rate constant.

In this experiment, the reaction is so conducted that the total volume of the reaction mixture is
effectively constant and the iodide is also at constant concentration since it is always regenerated
by the reaction. Hence the reaction between the iodide and the peroxide reduces to pseudo – first
order, the differential rate law being now given by

- d [H2O2 ] = k 1 [HI] [H2O2 ]

dt

where k 1 is the first order rate constant. If [H2O2 ]0 is the initial concentration of hydrogen
peroxide, integration of the equation above gives

In [H2O2 ] = - k 1 t + In [H2O2 ]0

The concentration of hydrogen peroxide that remains at time t, i.e., [H2O2 ] can be determined by
titration the iodine liberated against sodium thiosulphate.

I2 + 2 Na2S2O3 Na2S4O6 + 2 NaI

The value of k 1 can then be obtained from a plot of In [H2O2 ] versus t. The second order rate
constant k 2 is related to k 1 by

k 1 = k 2 [HI] 0

46
where [HI] 0 is the initial concentration of hydrogen iodide. The activation energy Ea of the
reaction can be calculated from the Arrhenius equation
k = A exp - Ea
RT

Thus,
ln K1” = Ea T2 - T1
K1’ R T1 T2

Materials

 A 2-volume solution of H2O2

 Sulphuric acid, made by mixing 1 volume of conc. acid with 2 volume of water
 0.1M sodium thiosulphate solution
 Potassium iodide
 Freshly prepared starch solution

Apparatus
 Pipette , stoppered conical flask, burette, graduated cylinder, test tube, stopwatch.

Procedures

1. Determination of the molarity of H2O2

Pipette 20cm3 of the sulphuric acid into a stoppered conical flask and dilute to 100cm3 with
distilled water. Add and dissolve 2g of potassium iodide. Add 10 cm3 of the hydrogen peroxide
solution, mix by shaking and then allow the whole to stand for about 10 minutes. Titrate the
liberated iodine with the standard thiosulphate solution until the solution turns pale yellow. Add
a few drops of starch solution and continue the titration to discharge the blue colour. Repeat the
procedure again.

2. Kinetic run

Dissolve 1g of potassium iodide in 250 cm3 of distilled water contained in a 500 cm3 conical
flask. Add by means of a graduated cylinder 15 cm3 of sulphuric acid. Mix well and thermostat
the flask at 30oC.

47
Put into two separate test tubes, with the aid of pipettes, 10 cm3 of hydrogen peroxide solution
and 5 cm3 of starch solution respectively. Immerse these tubes also in the water bath. While
waiting for thermal equilibrium, arrange a burette above the conical flask. Fill the burette with
sodium thiosulphate. Set the stopwatch to zero time. Pour into the conical flask the contents of
the two test tubes, first the starch solution and then the hydrogen peroxide. Mix well and start the
time. Run from the burette directly into the solution 5 cm3 of the 0.1M thiosulphate solution and
mix well. The blue colour of the starch-iodine complex, which develops on addition of hydrogen
peroxide solution, will now discharged. After some time, the blue colour will suddenly reappear;
the exact time at which this happens must be recorded.

Run in another known portion of thiosulphate solution. The blue colour is again discharged and
then reappears. Note the time of reappearance of the blue colour. Proceed in this way with timing
the reappearance of the blue colour. It should be realized that it is the reappearance of the blue
colour which must be timed and not the addition of the thiosulphate which should, however, be
added with as little delay as an accurate volume measurement will allow. Note the temperature
of the solution before and after the experiment and take the mean as the temperature of the
experiment.

Repeat the whole procedure at 40oC.

Treatment of Data

For each temperature, tabulate as follows

Total titrant volume Total time from [H2O2 ] In [H2O2 ]

Vt (cm3) beginning, t (s) (mol/l)
5
10
15
20
23
26
29
32
34
36
38
40

The term [H2O2 ] represent the concentration of hydrogen peroxide that remains at time t. It can
be obtained for each of the total volume of 0.1M thiosulphate solution required for titration. Plot
In [H2O2 ] versus t and calculate k 1 and hence k 2 for each temperature.

Calculate the activation energy Ea. Compare your results with those published earlier. Indicate
clearly the reference (s) used.

48
EXPERIMENT 21

KINETICS STUDY OF THE HYDROLYSIS OF METHYL ACETATE BY ACID-BASE

TITRATION.

Introduction

The hydrolysis of methyl acetate presents several interesting aspects. The reaction, which is
extremely slow in pure water, is catalyzed by hydrogen ion

K1
+
CH3COOCH3 + H2O + H CH3COOH + CH3OH + H+
K2

This reaction is reversible so that the net rate of hydrolysis at any time is the difference between
the rates of the forward and reverse reaction, each of which follows the simple rate law of the
form

- d [A] = k [A] [B ] ………………………………………………….(1)

dt

Thus,

- d [CH3COOCH3] = k 1 [CH3COOCH3] [H2 O] - k 2 [CH3COOH] [CH3OH]……. (2)

dt

where k 1 and k 2 are the rate constant for the forward and reverse reactions respectively. For
dilute solutions, water is presents in such large excess that its concentration undergoes only a
negligible change while that of methyl acetate is changed considerably. Therefore, equation (2)
may be written as

- d [CH3COOCH3] = k 1 [CH3COOCH3] - k 2 [CH3COOH] [CH3OH]………………(3)

dt

In the early stages of hydrolysis, the concentrations of acetic acid and methanol remain small
enough to be ignored and the reactions kinetics then appears to be of the first order, i.e.,

- d [CH3COOCH3] = k 1 [CH3COOCH3]………………………………………………(4)

49
 dt

The value of k 1 can be determined by one of the methods conventional for first order reactions.
In this experiment, the concentration of methyl acetate at a given time is determined by titration
of samples with a standard sodium hydroxide solution using phenolphthalein as an indicator.

Evaluation of k 1 at two different temperatures permits the calculation of the activation energy Ea
for the forward reaction. From the Arrhenius equation

k1 = A exp - Ea
RT

After integration

ln K1” = Ea T2 - T1
K1’ R T1 T2 …………………………………………………………………… ( 6)

Where K1” and K1’ are the rate constant for the forward reaction at temperature T1 and T2
respectively.

Materials

 Methyl acetate
 0.2M sodium hydroxide solution
 1.0M Hydrochloric acid
 Distilled water
 Phenolphthalein

Apparatus

 Burette, conical flask, pipette, beaker, test tube, thermostat, stopwatch

Procedures

1. Standardization of sodium hydroxide solution

Titrate 5cm3 of 1.0M hydrochloric acid with sodium hydroxide solution using phenolphthalein as
an indicator to determine the exact molarity of the sodium hydroxide. Repeat the titration for
another two portions of 5cm3 the acid.

50
2. Kinetics run

Measure 10cm3 of methyl acetate into a test tube and thermostat this at 30oC. Measure 100cm3 of
the hydrochloric acid into a conical flask and place this into the same water bath. When thermal
equilibrium has been reached (10 or 15 minutes should suffice). Pipette 5cm3 of the methyl
acetate into the acid, and start the timing when the pipette is half emptied. Shake the reaction
mixture for through mixing. As soon as possible, withdraw a 5cm3 aliquot of this mixture from
the flask and run into a conical flask containing 50cm3 of distilled water.

This dilution with water slow down the reaction considerable, but the solution should be titrated
at once; the error can be further reduced by chilling the water in an ice bath. Record the time
when the pipette is half emptied into the water in the titration flask. Titrate immediately using
phenolphthalein as indicator. Note the titrant volume. Additional samples are taken at 10 minutes
intervals for an hour, then at 20 minutes intervals for half an hour.

Repeat the same procedure for the kinetics run at 50oC. Because of the higher rate of reaction at
higher temperature, take the samples at 5 minutes intervals for 20 minutes, at 10 minutes
intervals for half an hour, and then 20 minutes intervals for half an hour.

Treatment of data

For each temperature, tabulate the results as follows

t (minute) Titrant volume V∞ - Vt (cm3) ln (V∞ - Vt )

Vt (cm3)

In this table, Vt is the titrant volume at time t. This measures the number of moles of
hydrochloric acid and acetic acid present in the 5cm3 aliquot of the reaction mixture at time t.
V∞ represents the final volume per 5cm3 aliquot if the hydrolysis were complete. Then V∞ - Vt
measures the number of moles of methyl acetate remaining per 5cm3 aliquot at time t, because
one molecule of acetic acid is produced for each molecules of methyl acetate hydrolyzed. The

51
corresponding concentration of methyl acetate in moles per dm3 is then N (V∞ - Vt ) / 5, where
N is molarity of the sodium hydroxide solution.

Calculation of V∞

If the reaction actually proceeds to completion, V∞ be measured directly by titration of an aliquot

from the equilibrium mixture. However, an appreciable amount of un-hydrolyzed methyl acetate
is present at equilibrium, so V∞ cannot be determined experimentally and must be calculated

The value of V∞ is given by the sum of two terms i.e,

V∞ = Volume of sodium hydroxide required to neutralize the hydrochloric acid in 5cm3 of

the reaction mixture

Volume of sodium hydroxide required to neutralize the acetic acid produced by

complete hydrolysis of 1 mol of methyl acetate contained in 5cm3 of the reaction
mixture

Let Vs be the volume of the solution initially formed by mixing 100cm3 of 1M hydrochloric acid
with 5cm3 of methyl acetate. This volume is 104.6cm3 rather than 105cm3 because the solution is
not ideal. Let Vx be the volume of sodium hydroxide required to neutralize a 5cm3 aliquot of the
original 1M hydrochloric acid. Then, the volume required to neutralize the hydrochloric acid in
5cm3 of the reaction mixture at any time is 100 Vx / Vs, on the assumption that the total volume
of the reaction mixture remains constant as the hydrolysis proceeds.

The weight of 5cm3 of methyl acetate is 5d2 where d2 is the density of methyl acetate ( 0.9273 at
25 oC , 0.9141 at 35 oC ) and the number of moles in this 5cm3 sample is 5d2 / M2 where M2 is
the molecular weight ( M2 = 74.08). the number of moles of methyl acetate initially present in
any 5cm3 aliquot of the reaction mixture is

5d2 5 = 25d2
M 2 Vs M2 Vs

Since 1000 / N cm3 of sodium hydroxide of molarity N is required to titrate the acetic acid
produced by hydrolysis of 1 mol of methyl acetate,

1000 25d2 = 25000d2

N M2 Vs N M2 Vs

cm3 will be required for the titration of the acetic acid produced by complete hydrolysis of the
methyl acetate originally contained in any 5cm3sample of the reaction mixture. The volume of

52
sodium hydroxide solution V∞ required to titrate both the hydrochloric acid and the acetic acid
produced by complete hydrolysis of the methyl acetate in a 5cm3 sample of the reaction mixture
is then

V∞ = 100 Vx + 25000d2
Vs N M2 Vs ……………………………………… (9)

Calculate the value of V∞ for each temperature using expression (9).

Plot a graph of ln (V∞ - Vt ) versus t and calculate the rate constant from the slope in
accordance with the expression

- ln C = kt + constant

53
EXPERIMENT 22

CRYOSCOPY : DETERMINATION OF RELATIVE MOLECULAR MASS BY

ENDPOINT CRYOSCOPY

Objective

To determine the relative molecular mass of unknown compound by endpoint cryoscopy.

Introduction

The freezing point of a dilute solution is lower than that of the pure solvent if the solid which
freezes out of solution is pure solvent and not a solid solution. Under these conditions the
lowering of the freezing point is proportional to the mole fraction of the solute in solution. If the
solution is very dilute, this relationship can be expressed as

Δ T = k [W (solute) / M (solute)] … (1)

where ΔT = depression of freezing point

k = cryoscopic constant (freezing point depression constant)

W (solute) = mass of solute per 1000 g of solvent

M (solute) = molar mass of solute

In this experiment, the freezing point is determined by the method called end point cryoscopy. A
solution of known concentration is partly frozen and then allowed to melt slowly whilst being
stirred so as to maintain thermal equilibrium. The temperature rises slowly until all solid has
melted as heat of fusion is taken up to convert solid to liquid. The plot generally shows two
linear branches from the intersection of which the freezing point of the solution can be obtained.

54
Apparatus and Materials

Boiling tube, salt / ice / water bath, stopwatch, thermometer (-20 ºC to + 30 ºC, graduated in 1 /
10 ºC), stirrer, 20 cm3 and 2 cm3 pipettes (both fitted with suction bulb), benzene, naphthalene,
unknown liquid.

Experimental Procedure

Benzene is used as the solvent in this experiment because it is readily available, possesses a
convenient freezing point, and has a relatively large cryoscopic constant.

a) Determination of freezing point of pure solvent. Pipette exactly 20 cm 3 of benzene into a

pyrex boiling tube and cool it in a salt / ice / water bath until about one half of it has
frozen. Then clamp it vertically, insert a (1 / 10 ºC) thermometer, stir gently and note the
temperature at 1 / 2 minute intervals until all the solid has melted and then for a further 3
minutes. The melting portion of the (temperature versus time) curve should be flat for a
pure substance.

b) Determination of cryoscopic constant of benzene. The freezing point of pure benzene (T-
0) is obtained in (a). Add an accurately known mass of naphthalene (ca. 1.0 g) to the 20
cm3 of benzene used in (a) and determine the melting curve for the solution as described
in (a).

c) Determination of relative molecular mass of unknown compound. Pipette exactly 2 cm3

of the unknown liquid into a boiling tube containing exactly 20 cm3 of benzene.
Determine the freezing point of this solution as described in (a) ( = Tu).

Results and Calculations

The result from (a) provides the freezing point of pure benzene (T0). The result from (b) provides
the freezing point of a solution of naphthalene of known concentration in benzene (T).

Knowing ΔT (T = T0 – T) and W (naphthalene) for this solution, it is possible to calculate k for

benzene from equation (1). M (naphthalene) = 128.3 g; density (benzene) = 0.879 g cm-3 at 20
ºC.

The freezing depression of the unknown solution (T0 – Tu) is known from (c). k and W (unknown
solute) are also both known, so that it is possible to determine the molar mass of the unknown
from equation (1). (Density of unknown liquid = 0.861 g cm-3 at 20 ºC).

55
56