CHEMISTRY

Escuela Politécnica de
Ingeniería de Gijón
Universidad de Oviedo EXPERIMENT 4

Chemical KINETICS and Chemical EQUILIBRIUM

OBJECTIVE: Observe and discuss the chemical nature of endothermic and exothermic
processes. Observe the chemical nature of redox reactions and complex-ion formation
reactions.

Q1. Write down the name of the reagents listed on the following table.

MATERIAL REAGENTS NAME

1 beaker of 50 mL HCl(aq) 10 M
1 graduated cylinder HCl(aq) 2M
1 test tube rack with 8 test tubes MnSO4(aq)
1 stirring rod FeCl3(aq) 0.1 M
test tube clamps KMnSO4(aq) 0.1 M
1 wash bottle NH4SCN(aq) 0.1 M
pH paper HOOC-COOH(aq)
1 dropper Fe nails and filings
1 stopper Zn pellets
1 thermometer

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4.1. Chemical EQUILIBRIUM

Thermodynamic equilibrium for a simple system (mixture of substances) means mechanical

equilibrium (constant pressure), thermal equilibrium (constant temperature), and chemical
equilibrium (fixed composition).

For a chemical reaction such as:

a A + b B + .....  p P + q Q ....
we have learned that: (i) at equilibrium ΔG = 0; and, (ii) if a system is at equilibrium Q = K.
Therefore, we can write that at equilibrium,

ΔG = ΔGº + RT ln K

which means that

ΔGº = -RT ln K

Where ΔGº is the standard Gibbs energy change based on the conversion of reactants in their
standard states to products in their standard states.

The constant, K, is the thermodynamic equilibrium constant. It is temperature dependent and it

is directly related to the equilibrium composition of the system. The constant K is related to
equilibrium reactants and products molarities:

K equil 
P Q ...
p q

Aa Bb ...

These and other thermodynamic expressions are very useful for predicting equilibrium
composition. But, they are also useful for predicting the response of a system in chemical
equilibrium if it is subjected to small disturbances, that is, to small changes in composition,
temperature, pressure.

Le Châtelier’s principle states that when a system is subjected to a change in temperature,

pressure or concentration of a reacting species, the system responds by attaining a new
equilibrium that partially offsets the impact of the change.

In the experiments that follow, the empirical meaning of Le Châtelier’s principle will be verified.

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A complex ion is a polyatomic cation or anion composed of a central metal ion to which other
groups (molecules or ions) called ligands are bonded. Coordination compounds are substances
containing complex ions.

In an aqueous solution of Fe(III), for example FeCl3(aq), Fe3+ ions form a octahedral complex ion
with six water molecules that act as metal ligands.

This coordination compound, [Fe(H2O)6]3+, it is a chemical

species with its own physical and chemical properties.
[Fe(H2O)6]3+ in the presence of thiocyanate anions, SCN-, react
forming the complex ion [Fe(H2O)5SCN]2+.
This complex ion formation reaction can be detected as a color
change.

Q2. Write the balanced ionic equation to represent the expected reaction between [Fe(H2O)6]3+
and the thiocyanate ions SCN-.

Q3. Write the thermodynamic equilibrium constant, K, expression for the between the iron (III)
chloride and the ammonia thiocyanate.

Experimental Procedure

1. Place 2 drops of 0.10 M FeCl3 in a test tube. Record the color of the Fe(III) salt solution.

2. Add 4 drops of 0.10 M NH4SCN. Stir the solution until it is thoroughly mixed. Record the
color of the formed [Fe(H2O)5SCN]2+ complex. Is this a fast or slow reaction?

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Both reactants are electrolytes and in aqueous medium they are dissociated into ions. SCN- ligand
replace water ligand to produce the [Fe(H2O)5SCN]2+ ion. This is virtually an instantaneous reaction
in both directions (~ 109s), a fast equilibrium.

In this experiment you will observe shifts in equilibrium system when conditions such as
concentration and temperature and temperature are changed. The colored substances are used to
allow you to determine the direction of equilibrium shifts based on color changes.

3. Dilute the obtained solution (step 2) with distilled water until its color is pale red, almost
orange. Divide the solution into five roughly equal parts in five test tubes. Keep one test
tube as a color control for comparison.

4. Add 2 drops of the 0.10 M FeCl3 solution to the second test tube. Record your observation.

5. Add 2 drops of 0.10 M NH4SCN solution to the third test tube. Record your observation.

Q4. Based on your observations, and using the principle of Le Châtelier, discuss the results.

Q5. Consider that the temperature remains constant. Will have changed the value of K?

Q6. What would happen if a very small amount of NH4Cl is added to the system?

Next, the effect of temperature on the chemical equilibrium will be checked.

6. Prepare an ice bath in a beaker, and place there the forth test tube.

Q7. In which direction will the system shift when the temperature is decreased?

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 7. Heat the content of the fifth test tube on a Bunsen burner.

Q8. In which direction will the system shift when the temperature is increased?

Q9. According to Le Châtelier principle, how can a reaction be determined to be endothermic or

exothermic based on equilibrium shifts? Justify your answer.

4.2. Chemical KINETICS

In the experiments that you just performed, and that have allowed you to appreciate some
thermochemical aspects, you have carried out several chemical reactions in aqueous solutions
whose reaction rate was very high. For practical purposes, you might consider such reactions as
instantaneous. However, this is not the general trend and chemical changes exhibit a wide range of
reaction rates. Why?

First of all because a chemical reaction requires energy, activation energy: the minimum kinetic
energy that molecules must bring to their collisions for a chemical reaction to occur.

Temperature, which is an index that indicates the average kinetic energy of molecules and ions, is
an important factor to control the reaction rate.

In addition, reactants concentration is also crucial. For example, if the concentration of reactants is
very low, the frequency with which the reactant molecules collide decreases, leading to decreased
rates. Also, if the reactants have different physical states (solid-liquid, for example), the reaction
rate increases if the surface area of the solid is increased.

In the experiments that follow, the effect of the factors affecting the reaction rate will be examined.

4.2.1. Effect of Reactants Concentration

Redox reactions are electron transfer reactions. Redox reactions are reactions in which one
species is reduced and another is oxidized. Therefore the oxidation state of the species involved
must change.

The following chemical equation chemistry illustrates the oxidation of zinc (Zn) in acid medium.

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 Oxidation Half-Reaction
Zn(s)  Zn2+(aq) + 2 e-

Reduction Half-Reaction
H+(aq) + 2 e-  H2(g)

Experimental Procedure

1. Place a Zn pellet in two test tubes.

2. In one of the test tubes, add 2 M HCl until the Zn pellet is completely covered. In the
second test tube, add a similar volume of 10 M HCl.

Q10. What gaseous product is formed during the reaction?

Q11. According to your observations, indicate how an increase in HCl concentration affects the
reaction rate.

Q12. Indicate if equilibrium between reactants and products can be achieved for this chemical
reaction.

4.2.2. Effect of Contact Surface Area

As you have seen, the attack of a metal by an acid is a reaction that occurs in a heterogeneous
system, the metal being in solid phase and the acid in aqueous solution. Let’s check the influence
of the contact surface area between the solid phase and the aqueous phase on the reaction rate.

Experimental Procedure

1. Place an iron nail into a test tube and add 10 M HCl in order to cover half of it.
2. In a second test tube introduce a small amount of iron filings. Add a similar volume of 10 M
HCl. Record your observations.

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Q13. Fe (s) is oxidized to an oxidation state +2 due to the effect of hydrochloric acid. Write the
corresponding chemical equation, identifying the changes in the oxidation states and the
oxidant-reducing species.

Q14. According to your observations, indicate how the contact surface area affects the reaction
rate.

Q15. A secondary reaction that takes place during the reaction of HCl and iron filings is the
formation of H2S (g). Could you explain why?

Q16. Consider that in both cases the mass of used iron is the same. Do you think that the final
amount of released gas will vary? Justify your answer.

4.2.3. Effect of Temperature

During this experiment the oxidation of oxalic acid with permanganate will be carried out. A very
common oxidizing agent: the permanganate anion MnO4- (easily recognized in aqueous solution
due to its characteristic intense violet coloring) will be used.

Q17. Which is the oxidation state of manganese in this anion?

The high oxidation state reached by manganese indicates that manganese reduction, that is its
gain of electrons, is favorable. The stable reduced form of manganese in aqueous solution is Mn2+.

Oxalic acid is a typical weak organic acid. It is a diprotic acid. Look at the structure of its basic form
(oxalate) with two negative charges.

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 oxalic acid

oxalate ion

This dianion, can be oxidized by transferring two electrons and leading to the formation of two
molecules of carbon dioxide, the most stable and completely oxidized form of carbon.
Permanganate anion oxidize the oxalic acid. The ionic equation corresponding to this reaction is:

16 H+ + 2 MnO4(aq) + 5 C2O42(aq) → 2 Mn2+(aq) + 10 CO2(g) + 8 H2O

Experimental Procedure

1. Place 2 mL of the oxalic acid solution in two test tubes.

2. In the first test tube, add 5 drops of KMnO4 solution, and gently shake the test tube to mix
the contents. Record your observations.

Q18. Is the redox reaction taking place?

3. In the second test tube, add 5 drops of KMnO4 solution, and heat it on a Bunsen burner.
Record your observations. Keep alert !!!

Q19. What differences in behavior have you observed between the reaction at room temperature
and the reaction at high temperature?

As you have seen, the temperature significantly affects the reaction speed. In fact, for aqueous
solution reactions, an increase of temperature of 10 ºC doubles the reaction rate.

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4.2.4. Effect of a Catalyst

A catalyst is a substance that changes the speed of a chemical reaction without undergoing a
permanent change itself.

Experimental Procedure

1. Place 2 mL of the oxalic acid solution in two test tubes.

2. Add 5 drops of KMnO4 solution to each test tube, and gently shake them to mix the
contents.
3. Keep one of the test tube as control. Add 1 mL MnSO4 solution to the second one.

Q20. According to your observations, what effect has the presence of the MnSO4 on the
reaction?

Q21. It is said that MnSO4 acts as an autocatalyst in the oxalic oxidation by the permanganate.
Which can be the reason?