MA, PAULINE Date Performed: 1 OCTOBER 2014

NACIONGAYO, DANIELLE Date Submitted: 8 OCTOBER 2014

TEDERA, YVES

LE CHATELIERS PRINCIPLE
Experiment No. 4

I. Results
A. Gaseous Equilibrium
Nitrogen dioxide (NO
2
), a reddish brown gas, was produced by adding
pieces of copper wires to concentrated HNO
3
in an Erlenmeyer flask. The reaction
between the copper and nitric acid is given by this equation:

Cu + 4HNO
3
Cu (NO
3
) + 2H
2
O + 2NO
2

The gas was collected using a glass syringe. Pressure was then applied to
the gas until it reached the 8ml mark of the syringe. Upon the addition of
pressure, the gas changed into a lighter color. The appearance of the gas inside the
syringe is shown in figures 1 and 2.


Fig. 1: 12ml gas collected Fig. 2: Pressure applied to the gas

The gaseous equilibrium is given by this equation:

2NO
2
N
2
O
4

The syringe of gas was plunged into beakers with different water
temperatures. After plunging the syringe inside the beaker with cold water, the
gas changed into a lighter color (Fig. 3). And the color of the gas turned darker
after it was plunged in the hot water (Fig. 4).


Fig. 3: Cold Water Fig. 4: Hot Water

B. Common Ion Effect
Acetic acid (HOAc) was placed in an Erlenmeyer flask and was added
with methyl reed indicator. A pinch of sodium acetate was added to the flask and
mixed. The reaction inside the flask is given by this reversible equation:

HOAc + H
2
O OAc
-
+ H
3
O
+

Upon the addition of sodium acetate, no change of color was observed.
Both solutions had a light pink shade (Fig. 5 and 6).


Fig. 5: HOAc only Fig. 6: HOAc with sodium acetate

C. Complex Ion Equilibrium
A solution of 1ml each of 0.1M FeCl
3
and 0.1M KSCN was prepared and
diluted with enough water to make it 100ml. The resulting solution was divided
into four test tubes. The solution has an orange color. The reaction is defined by
this equation:

FeCl
3
+ KSCN FeSCN
2+
+ K
+
+ Cl
-


The four test tubes were added with different compounds. For test tube 1,
Fe (NO
3
)
3
was added; for test tube 2, NH
4
SCN was added; for test tube 3, KCl
was added; and for test tube 4, Na
2
PO
4
was added. Color changes were observed.
Test tubes 1, 2, 3 and 4 resulted to a darker orange, red, cloudy white and
colorless solution, respectively (Fig. 7).


Fig. 7: Solutions with different compounds added

FeSCN
2+
is the complex ion. The complex ion equilibrium is given by this
equation:
Fe
3+
+ SCN
-
FeSCN
2+

D. Chromate-Dichromate Equilibrium
The colors of K
2
CrO
4
and K
2
Cr
2
O
7
solutions were observed. Test tubes 1
and 2 contained K
2
CrO
4
while test tubes 3 and 4 contained K
2
Cr
2
O
7
. Test tubes 1
and 2 have test tubes 3 and 4 have an orange color. 1M NaOH was added to test
tubes 1 and 3 while 1M HCl was added to test tubes 2 and 4. Color changes
occurred (Fig. 8 and 9). Table 1 summarizes the color changes that occurred to
each solution.


Fig. 8: Test tubes 2 and 4 Fig. 9: Test tubes 1 and 3

Table 1: Color Changes
TEST TUBE INITIAL COLOR FINAL COLOR
1 Yellow Yellow
2 Yellow Orange
3 Orange Yellow
4 Orange Orange

The chromate-dichromate equilibriums are given by these equations:

2CrO
4
2-
+ H
2
O
-
Cr
2
O
7
2-
+ 2OH
Cr
2
O
7
2-
+ H
2
O 2CrO
4
2-
+ 2H
+

II. Discussion
A. Gaseous Equilibrium
A dynamic equilibrium occurs when you have a reversible reaction in a
closed system. Nothing can be added to the system or taken away from it apart
from energy. At equilibrium, the quantities of everything present in the mixture
remain constant, although the reactions are still continuing. This is because the
rates of the forward and the back reactions are equal.
If you change the conditions in a way which changes the relative rates of
the forward and back reactions you will change the position of equilibrium.
Le Chatelier's principle states that if a dynamic equilibrium is disturbed by
changing the conditions, the position of equilibrium shifts to counteract the
change to reestablish equilibrium. If a chemical reaction is at equilibrium and
experiences a change in pressure, temperature, or concentration of products or
reactants, the equilibrium shifts in the opposite direction to offset the change.
According to the same principle, if the pressure is increased, the position
of equilibrium will move so that the pressure is reduced again. Pressure is caused
by gas molecules hitting the sides of their container. The more molecules in the
container, the higher the pressure will be. The system can reduce the pressure by
reacting in such a way as to produce fewer molecules.
In the experiment, the product side of the equation has 1 mole of a gas; the
reactant side has 2 moles. Increasing the pressure favored the side with the fewest
moles of gas, so the equilibrium shifted to the right (the forward reaction was
favored). Thus, the light colored gas which is N2O4 was formed.
Same goes with temperature. A change in the analytical amount of a
reactant or product produces a stoichiometric stress on the system. A change in
temperature also constitutes a stress on the system.
An increase in temperature is the result of the flow of heat into the system.
Conversely a flow of heat out of the system reduces the temperature. Suppose
an exothermic reaction is at equilibrium, and then the temperature of the system is
increased. The increase in temperature corresponds to introducing heat into the
system. This influx of heat pushes the system away from equilibrium and nature
restores equilibrium by removing some of this additional heat. Because the
reaction is exothermic, the reaction produces heat when it proceeds in the forward
direction. Le Chatelier's Principle states that the system will react to remove the
added heat, thus the reaction must proceed in the reverse direction, converting
products back to reactants. Conversely if the temperature of the system were
decreased (heat removed from the system), the system would react in a direction
that opposed the removal of the heat. The forward reaction would thus occur to
release heat in an attempt to offset the heat that was removed from the system.
When the temperature is changed the equilibrium shifts. Cooling the gas caused a
shift towards the light colored gas, N2O4, which should be colorless when pure
but can be blue-green due to impurities such as N2O3. The equilibrium reaction is
exothermic.
2 NO2 N2O4 + heat

In the experiment, heating the gas produced the dark brown gas, which is
NO2 or the reverse reaction is favored. Conversely, cooling the gas produced the
light colored gas, N2O4. Therefore, a forward reaction is favored.

B. Common Ion Effect
Le Chatelier's Principle states that if equilibrium becomes unbalanced, the
reaction will shift to restore the balance. If a common ion is added to a weak acid
or weak base equilibrium, then the equilibrium will shift towards the reactants, in
this case the weak acid or base.
The common-ion effect is used to describe the effect on an equilibrium
involving a substance that adds an ion that is a part of the equilibrium. Adding a
common ion prevents the weak acid or weak base from ionizing as much as it
would without the added common ion. The common ion effect suppresses the
ionization of a weak acid by adding more of an ion that is a product of this
equilibrium. Also, adding a common ion decreases solubility, as the reaction
shifts toward the left to relieve the stress of the excess product. Adding a common
ion to a dissociation reaction causes the equilibrium to shift left, toward the
reactants, causing precipitation.
Sodium acetate is a strong electrolyte so it dissociates completely in the
solution. Acetic acid is a weak acid so it only ionizes slightly. According to Le
Chatelier's principle, the addition of acetate ions from sodium acetate will
suppress the ionization of acetic acid and shift its equilibrium to the left. Thus the
percent dissociation of the acetic acid will decrease and the pH of the solution will
increase. The ionization of an acid or a base is limited by the presence of its
conjugate base or acid.
This will decrease the hydrogen ion concentration and thus the common-
ion solution will be less acidic than a solution containing only acetic acid.

C. Complex Ion Equilibrium
When a metal ion reacts with a Lewis base in solution a complex ion is
formed. This reaction can be described in terms of chemical equilibria.
A complex ion is comprised of two important parts: the central atom and
its surrounding ligands. The central atom can be any metallic ion (usually a
transition metal). The ligands are any combination of anions that can donate an
electron pair, effectively meaning they are all Lewis bases. When combined they
form coordinate covalent bonds.
The discussion of complex ion equilibrium is no different from the
common ion equilibrium. The concentration of a certain ion is increased. In the
experiment, ferric and thiocyanate ions increased in amount. According to Le
Chatelier's principle, to restore equilibrium, the reaction will shift in the forward
direction to cancel the effect of change in concentration. Thus, it favored the
reaction forming the deep-red complex, FeSCN
2+
.
When KCl was added, K
+
and Cl
-
ions increased in concentration. The
equilibrium will shift to the reverse reaction. The red colored solution changed
into a lighter intensity. However, when H
2
PO
4
was added, it yielded a colorless
solution. It means that it has no effect in the equilibrium reaction.

D. Chromate-Dichromate Equilibrium
When solid potassium chromate, K
2
CrO4 is dissolved in water it forms a
yellow solution. When solid potassium dichromate, K
2
Cr
2
O
7
is dissolved in water
the resulting solution is orange. The colors come from the negative ions: CrO
4
2-
(aq) and Cr
2
O
7

2-
(aq). However, in solution these ions are actually in equilibrium
as indicated by the equation:
2 CrO
4

2-
(aq) + 2 H
+
(aq) Cr
2
O
7

2-
(aq) + H
2
O (l)

Le Chateliers Principle states that If a stress is applied to a reaction at
equilibrium, the reaction will shift to offset the stress applied. The addition of
hydrogen ions or hydroxide ions constitutes a stress, as does the removal of either
ion, and so it can be expected that the above equilibria will shift in response to
concentration changes in these ions. For example, in eqn. 1, if [H
+
] is increased by
adding HCl, there are more ions available for reaction and the reaction will favour
the formation of products. Conversely, if [H
+
] is decreased (by adding OH
-
) there
are fewer ions available for the forward reaction and the reaction shifts reverse to
favor reactant formation.

III. Answers
A. Gaseous Equilibrium
1. Generating NO2 must be operated under the fume hood because it is toxic. Also,
N2O4 is toxic, corrosive, and combustible. An increase in pressure will result in a
lighter colored gas (Fig. 2) since it favors the formation of the lesser number of moles
of substances, thus, N2O4 increased in concentration or was produced. Decreasing
the pressure favors the formation of the greater number of mole of substances, thus,
NO2 is produced which is the darker colored gas.

2. Cu + 4HNO
3
Cu(NO
3
) + 2H
2
O + 2NO
2



B. Common Ion Effect
Increasing the concentration of OAc- will favor the backward reaction. This
would result to a lower concentration of H3O+. A decrease in concentration of
H3O+ means the solution obtained an increase in pH value making its color turn
to red violet since methyl red at pH 4.2 is red violet while at pH 6.2 is yellow.


C. Complex Ion Equilibrium
1. Fe
3+
+ SCN
-
FeSCN
2+


2. The increase in the concentration of Fe3+ and SCN- resulted in the increase of
the concentration of the red colored complex, FeSCN2+. The color of the solution
darkened. The increase in the concentration of KCl resulted in the decrease of the
concentration of the red complex. Thus, a lighter red color was produced.
Na2HPO4 has no effect to the system thus, leaving a colorless solution.


D. Chromate Dichromate Equilibrium
1. Chromate ion has a yellow color while dichromate ion has an orange color.

2. 2CrO
4
2-
+ H
2
O Cr
2
O
7
2-
+ 2OH
-


3. An increase in concentration of OH- will favor the formation of chromate thus,
making the solution yellow.

4. Dichromate ion is produced.

5. Cr
2
O
7
2-
+ H
2
O 2CrO
4
2-
+ 2H
+


IV. Conclusion
Le Chateliers principle basically states that if stress is applied to a system at
equilibrium, the position of the equilibrium will shift in the direction that reduces the
stress to reinstate equilibrium. For example, if more reactants are added to the system,
the reaction will shift in the forward direction, and if more products are added, the
reaction will shift in the reverse direction. If heat is added to the system and the
reaction is exothermic, heat should be thought of as a product and the reaction will
shift to the left; if the reaction is endothermic and heat is added, the reaction will shift
to the right. The addition of pressure will cause a shift in the direction that results in
the fewer number of moles of a gas, while if pressure is relieved, the reaction will
shift in the direction that produces more moles of a gas.

V. References
Blauch, David N. (2009). Chemical Equilibria, Available online:
http://www.chm.davidson.edu/vce/equilibria/index.html
Clark, Jim, (2002). Le Chateliers Principle, Available online:
http://www.chemguide.co.uk/physical/equilibmenu.html
Harwood, William S., F. G. Herring, Jeffry D. Madura, and Ralph H. Petrucci.
General Chemistry Principles and Modern Applications. 9th ed. New Jersey:
Prentice Hall, 2007. 670-a32.
Mendham, J., Denney, R. C., Barnes, J. D., Thomas, M.J.K., Denney, R. C.,
Thomas, M. J. K. (2000), Vogel's Quantitative Chemical Analysis (6th ed.),
New York: Prentice Hall, ISBN 0-582-22628-7
Petrucci, R.H. & Harwood, W.S. (1998). General chemistry: Principles and
modern applications. (8th ed.) New Jersey: Prentice-Hall International