CHM213

PHYSICAL CHEMISTRY

LABORATORY MANUAL
 EXPERIMENT 1
THERMOCHEMISTRY
Objective:
a) To determine the heat capacity of calorimeter
b) To determine the heat of neutralisation

Background:
a) Determining the heat capacity of a calorimeter
A known weight of hot water (m, g) at T1oC is added to a known weight of cold water
(m2 g) at T2oC in a calorimeter.
Heat released by hot water = Heat absorbed by cold water & calorimeter
m1c(T1 – T3) = m2c(T3 – T2) + (T3 – T2)y
where c = specific heat of water, 4.184 J g-1 oC-1
T3 = final temperature of the mixture
y = heat capacity of the calorimeter

b) Determining the heat of neutralisation

A known weight of strong acid (ma g) at TAoC is mixed with a known weight of strong
base (mb g) at TBoC in a calorimeter. The final temperature of the mixture is TMoC
Heat released by the mixture
(𝑇𝐴+𝑇𝐵) (𝑇𝐴+𝑇𝐵)
= (ma + mb) c[TM - ] + y[TM – ]
2 2

Heat of neutralisation = Heat released / No. of moles acid or base used

Chemical:
2M HCL, 2M HNO3, 2M NaOH & 2M KOH

Apparatus:
Polystyrene cups with cover, thermometer, beakers and measuring cylinders

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Procedure:
Determining the heat capacity of a calorimeter:
a) Weigh the overlapping polystyrene cups (calorimeter).
b) Measure 50 mL of cold water and pour into the calorimeter.
c) Measure 50 mL of hot water (about 60oC) and its temperature.
d) Pour the hot water into the cold water. Cover immediately and stir using the
thermometer.
e) Note the maximum temperature reached by the mixture.
f) Weigh the calorimeter (without the cover and thermometer).
Determining the heat of neutralisation:
a) Weigh the above calorimeter (ma) (without the cover and thermometer).
b) Measure 50 mL of strong acid and pour into calorimeter. Weigh the calorimeter
containing the acid solution.
c) Measure 50 mL of strong base.
d) Measure the temperatures of the two solutions (TA) and (TB).
e) Pour the strong base into the calorimeter. Cover and stir with the thermometer.
f) Note the maximum temperature (TM) reached by the mixture.
g) Weigh the calorimeter (mb) (without the cover and thermometer).

Result:
a) Determining the heat capacity of a calorimeter
Weight of calorimeter ?
Weight of calorimeter + cold water ?
Weight of cold water (m2) 50.0 g
Temperature of cold water (T2) 17.4 oC
Temperature of hot water (T1) 40.5 oC
Weight of calorimeter + cold water + hot water ?
Weight of hot water (m1) 50.0 g
Maximum temperature (T3) 28.3 oC

b) Determining the heat of neutralisation

Weight of calorimeter ?
Weight of calorimeter + acid ?
Weight of acid (ma) 50.0 g
Temperature of acid (TA) 21.1 oC
Temperature of base (TB) 21.1 oC
Maximum temperature (TM) 31.5 oC
Weight of calorimeter containing both acid and ?
base
Weight of base (mb) 50.0 g

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Calculation:
I) Use the data above to calculate

a) The heat capacity of calorimeter

b) The heat of neutralisation for your set of strong acid-strong base pair

II) Tabulate the class result for the heat of neutralisation for the four possible
set of strong acid-strong base
Strong Acid Strong Base

Discussion:
III) Comment on the tabulated result as compared to the standard molar
enthalpy change of neutralisation for strong acid and strong base with a
value of -57.3 kJmol-1.

IV) Using the assumption that the density of the solution mixture in the same as
water, calculate heat of neutralisation for strong acid and strong base of
your set. Comment on the result obtained.

Conclusion:
Write the experimentally obtained value for
I) The heat capacity of calorimeter (y).
II) The heat of neutralisation for your set of strong acid-strong base pair.
III) The average value of the heat of neutralisation for every set of strong acid-
strong base pair.

Reference:
List 3-4 references

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 EXPERIMENT 2
CHEMICAL EQUILIBRIUM: LE CHATELIER’S PRINCIPLE

Objective:
To study the shift in equilibrium of reversible reactions using Le Chatelier’s Principle

Background:
Once a system has attached equilibrium, it is possible to change the composition of
the equilibrium mixture by changing the conditions of the reaction. The study of the
factors which alter the position of equilibrium is commercially important as many
industries will find the optimum conditions for reactions that give the best yields and at
the same time the lowest cost of production. The reaction system remains in dynamic
equilibrium only as long as the system remains isolated or closed where there is no
exchange of matter or energy between system and surroundings.
If the external conditions such as temperature, concentration and pressure or other
factors are changed, the equilibrium will shift to a new position of equilibrium. The
direction in which an equilibrium will shift when one of these changes is made can be
predicted by applying Le Chatelier’s principle. Le Chatelier’s principle states that when
a system at equilibrium is subjected to a change in temperature, pressure or
concentration of a reactant or product, the system will, if possible, shift its equilibrium
position so as to partially counteract the effect of the change
In this experiment, you will study the following reactions:

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Chemicals:
Phenolphthalein, 1.0 M NH4OH, solid NH4Cl, 1.0 M NaOH, 1.0 M CH3COOH, solid
NaCl, 1.0 M K2CrO4, 3.0 M HNO2, 0.1 M CuSO4, 0.02 M FeCl3, 0.2 m NH4SCN,
conc. NH3
Procedure:
1. Add 5 mL of water and 2 drops of phenolphthalein into a test tube. Add a few
drops of 1.0 M NH4OH. Observe the color of the solution. Add a few drops of
1.0 M CH3COOH until the color of the solution changes. Record the color
obtained.
2. Add 5 mL of water and 2 drops of phenolphthalein into a test tube. Add a few
drops of 1.0 M NH4OH. Observe the color of the solution. Divide the solution
into 2 portions. Add a little solid NH4Cl to one portion of the solution and shake
well. Compare the color of the two solutions.
3. Add 5 mL of water and 2 drops of phenolphthalein into a test tube. Add one
drop 0f 1.0 M NaOH. Divide the solution into 2 portions. Add a little NaCl to one
portion of the solution and shake well. Compare the color of the two solutions.
4. Add 3 mL of 1.0 M K2CrO4 to a test tube. Add 3.0 M HNO3 to the solution until
the color changes. Record your observations.
5. Add 3 mL of 0.1 M CuSO4 to a test tube. Add conc. NH3 drop by drop and shake
well. If a precipitate is formed, add more conc. NH3 until it dissolves. Add 3.0
M HNO3 to the solution until the color changes. Add conc. HNO3 drop by drop
and shake well until a permanent color is obtained. Record your observations.
6. Mix 2 mL of 0.02 M FeCl3 with 2 mL of 0.2 M NH4SCN in a beaker. Add 20 mL
of distilled water. Fill 5 test tubes with the above solution. Carry out the following
experiments with the 5 solutions. Record the result in table.
Experiment Color
a) Test tube 1 + 5 mL water
b) Test tube 2 + 5 mL FeCl3 (0.02 M)
c) Test tube 3 + 5 mL NH4SCN (0.2 M)
d) Test tube 4 + 5 mL water
Immerse the test tube in ice
e) Test tube 5 + 5 mL water
Immerse the test tube in hot water

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Result and Discussion
Tabulate your result in 3 columns as shown below
Procedure Observation Interference
1
2
3
4
5
6a)
6b)
6c)
6d)
6e)

Use Le Chatelier’s Principle to write in the inference column by explaining the changes
of color observed in all procedures. You should be able to make use of the equations
given in the background section. Identify carefully the factors affecting the shift in
equilibrium of reversible reactions such as concentration of acid and base (procedure
1 & 4), common ion effect (procedure 2 & 3), concentration of ligand (procedure 5,
6(a), 6(b) & 6(c)) and temperature (procedure 6(d) & 6(e))

Conclusion:
Conclude the overall obtained result by justifying the objective.

Reference:
List 3-4 references.

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 EXPERIMENT 4
ACID-BASE EQUILIBRIUM: Acid, Bases and Buffer Solution
Objective:
a) To measure the pH of solutions of different acidity and basicity
b) To determine the ionisation constant of a weak acid
c) To study the effect of dilution on the degree of ionisation
d) To study the properties of buffer solutions
Background:
There are several definitions of acids and bases:
Acid Base
Arrhenius Substance that produces Substance that produces
H3O+ in water OH- in water
Bronsted-Lowry Proton donor Proton acceptor
Lewis Substance that can Substance that can
accept a pair of electrons donate a pair of electrons

Every aqueous solution whether acidic, basic

or neutral contains both H+ and OH- ions.
The product of their concentrations is always
constant equal to 1.0 X 10-14 at 298 K.
[H+][OH-] = 1.0 X 10-14
pH is a measure of the acidity or basicity of a
solution.
pH = - log[H+]
The pH scale commonly in use ranges from
0 to 14.

The strength of an acid is determined by how far the equilibrium lies to the right.

HA H + + A-
The dissociation constant of the acid, Ka can be calculated as:

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 [𝐻+][𝐴−]
Ka = [𝐻𝐴]

A large Ka (about 10 to 109) indicates a strong acid; a small Ka indicates a weak acid.
Strong acids and strong bases dissociate in a solution almost completely. Hence the
dissociation studies are important only with respect to weak acids and weak bases.

The fraction of the total number of moles of an acid or base that dissociates into ions
in an aqueous solution when equilibrium is reached is called the degree of
dissociation. It is represented by the symbol α.

Ostwald’s dilution law is a relationship between the dissociation constant and the
degree of dissociation of weak acids or bases.
Consider a weak acid HA H+ + A-
Initial mol 1 0 0
Change -x +x +x
Mol at equilibrium 1-x x x
Conc. At equilibrium (1-x)/v x/v x/v

[𝐻+][𝐴−]
Equilibrium constant, Ka = [𝐻𝐴]
𝑥 𝑥
( )( )
𝑣 𝑣
Ka = 1−𝑥/𝑣

But concentration, c = 1/V

Ka = (c2 x2)/c – cx
Ka = (c x2)/1 – x
Assuming that x is very small, where 1 – x = 1, therefore Ka = cx2
A buffer is a solution that does not change its pH easily. One can add some acid or
base to a buffer and the pH does not change drastically.
A buffer solution is one in which there are two chemical species present:
a) One needs to be able to accept H+ ions and
b) The other needs to be able to donate H+ ions
Usually, buffers are made with a weak acid and its conjugate base (acidic buffer) or
a weak base and its conjugate acid (basic buffer).

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Chemical:
As shown in the table under the Results and Discussion section

Procedure:
a) Measuring pH of solutions
-Before any measurements are made, predict the pH values for each of the solutions
listed in the Results and Discussion section. Then you will measure the pH values of
the solutions. Fill in the results in the table provided.
b) Effect of dilution on α
-Prepare the solutions as required. Predict their pH values and then only measure the
pH. Fill in the results in the table provided.
c) Buffers
-Prepare the solutions as required. Predict whether solution no. 13 and 14 are buffers
or not. Measure the pH of all the solutions and fill in the results in the table provided.

Results and Discussion:

pH readings of the chemical solution used
Chemical solutions Predicted pH Measured pH
a) Hydrogen ion concentration: pH
1. Distilled water
2. Tap water
3. vinegar
4. milk
5. 0.1 M NH4OH
6. 0.1 M NH4NO3
7. 0.1 M NaCl
8. 0.1 M CH3COONa
9. 0.1 M CH3COONH4
b) Effect of dilution
10. 0.1 M CH3COOH
11. 5 mL 0.1 M CH3COOH + 5
mL H2O
12. 1 mL 0.1 M CH3COOH + 9 ml
H2O
c) Buffers
13. 5 mL 0.1 M CH3COOH + 5
mL 0.1 M HCl
14. 50 mL 0.1 M NH4OH + 50 mL
0.1 M NH4NO3
15. 10 mL of (14) + 6 mL of H2O

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 16. 10 mL of (14) + 5 mL of H2O
+ 1 mL 0.1 M HCl
17. 10 mL of (14) + 6 mL 0.1 M
HCl
18. 10 mL of (14) + 5 mL of H2O
+ 1 mL 0.1 M NaOH

Questions:
1. Classify solutions no. 1 – 14 in the experiment into any of these groups:
a) Strong acid
b) Strong base
c) Weak acid
d) Weak base
e) Buffer solution
Justify your answers.

2. Is the degree of ionisation affected by dilution? Explain.

3. What are the common ions that are found in solution no. 14?

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Conclusion:
Conclude the overall obtained result by justifying the objective.

Reference:
List 3-4 references.

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