NATIONAL UNIVERSITY OF COLOMBIA

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SCIENCE FACULTY - SCHOOL CHEMISTRY
Analytical Chemistry (3007421-01). First Quiz (10%). April 2015

NAME: HUGO ALEJANDRO MRQUEZ ARISTIZBAL

CARD: 1.017.231.914

1.
The authors of the article propose three alternatives to explain the effects of changes in
equilibrium systems, namely: The law of equilibrium, the reaction quotient and Van't Hoff
equation, which predict the direction in which a system in equilibrium changes when it is
disturbed. Explain briefly what constitutes each of these alternatives.

Law of Equilibrium:

The Law of Chemical Equilibrium is a relation stating that in a reaction mixture at equilibrium,
there is a condition (given by the equilibrium constant, Kc) relating the concentrations of the
reactants and products. For the reaction
+ cC + dD
[] []
=
[] []
For any given temperature, there is only one value for the equilibrium constant. Kc only changes if
the temperature at which the reaction occurs changes. If the value for Kc is very large, then the
equilibrium favors the reaction to the right and there are more products than reactants. The
reaction may be said to be "complete" or "quantitative." If the value for the equilibrium constant
is small, then the equilibrium favors the reaction to the left and there are more reactants than
products. If the value of Kc approaches zero the reaction may be considered not to occur. If the
values for the equilibrium constant for the forward and reverse reaction are nearly the same then
the reaction is about as likely to proceed in one direction and the other and the amounts of
reactants and products will be nearly equal. This type of reaction is considered to be reversible.

Reaction Quotient

The reaction quotient (Q) measures the relative amounts of products and reactants present during
a reaction at a particular point in time. The reaction quotient aids in figuring out which direction a
reaction is likely to proceed, given either the pressures or the concentrations of the reactants and
the products. The Q value can be compared to the Equilibrium Constant, K, to determine the
direction of the reaction that is taking place.
The main difference between K and Q is that K describes a reaction that is at equilibrium, whereas
Q describes a reaction that is not at equilibrium. To determine Q, the concentrations of the
reactants and products must be known. For a given general chemical equation:
+ cC + dD

[] []
[] []

If Q>K, then the reaction favors the reactants.

If Q<K, then the reaction favors the products.
If Q=K, then the reaction is already at equilibrium.

Vant Hoff Equation

The Van't Hoff equation in chemical thermodynamics relates the change in the equilibrium
constant, Kc, of a chemical equilibrium to the change in temperature, T, given the standard
enthalpy change, H, for the process.
The Van't Hoff plot, which is derived from this equation, is especially effective in estimating the
change in enthalpy, or total energy, and entropy, or amount of disorder, of a chemical reaction.

From the definition of Gibbs free energy

Where S is the entropy of the system, and from the Gibbs free energy isotherm equation, [5] and

These equations are combined to obtain

2.
Do a search in the literature of the effects of changes in concentration, volume, pressure
or temperature on chemical equilibrium systems.

Change in Concentration

Changing the concentration of a chemical will shift the equilibrium to the side that would reduce
that change in concentration. The chemical system will attempt to partially oppose the change
affected to the original state of equilibrium. In turn, the rate of reaction, extent and yield of
products will be altered corresponding to the impact on the system.

The only way the system can minimise the imposed change (i.e. the reactants concentration
increase) is to use up reactants by transforming them into products. This means, that for a while
the forward reaction is faster than the reverse reaction, so that the reactants concentration
decreases. As a consequence, the forward reaction slows down and due to the product
concentration increase, the reverse reaction rate increases until it becomes equal to the forward
reaction rate

Change in Temperature

The effect of changing the temperature in the equilibrium can be made clear by a) incorporating
heat as either a reactant or a product, and b) assuming that an increase in temperature increases
the heat content of a system. When the reaction is exothermic (H is negative, puts energy out),
heat is included as a product, and, when the reaction is endothermic (H is positive, takes energy
in), heat is included as a reactant. Hence, whether increasing or decreasing the temperature would
favor the forward or the reverse reaction can be determined by applying the same principle as
with concentration changes.
An increase in temperature constitutes a change which the system can minimise by a heat
consuming (endothermic) reaction. If this is the forward reaction, an increase in temperature will
shift the equilibrium to the right; if the forward reaction is exothermic (and hence the reverse
reaction endothermic), the shift will be to the left. In any case, the equilibrium shifts to the side
with the substances richer in energy. Of course a temperature decrease has the opposite effect.

Change in Pressure

Changes in pressure are attributable to changes in volume. The equilibrium concentrations of the
products and reactants do not directly depend on the pressure subjected to the system. However,
a change in pressure due to a change in volume of the system will shift the equilibrium.
The influence of pressure changes are only relevant to equilibria, in which gases are involved, since
liquids and solids are virtually incompressible. With gases, an increase of the pressure results in an
increase of the concentration. The product of the pressure and the volume of a gas under constant
temperature is constant. Doubling the pressure results in halving the volume and therefore
doubling the concentration. In this way, the effects of pressure changes can be defined using the
law of mass action.
According to Avogadros Law, the volume of a gas is proportional to the number of its molecules.
Thus, more molecules need more space - or, if the volume cant be increased, they exert a higher
pressure. If the number of gas molecules is different on the reactants and products side, the
system can minimise an increase in pressure by shifting to the side with less gas molecules.

3.
State one brief comment on the conclusions reached by the researchers who conducted
the so-called study of Hong Kong.
As the author says, Le Chteliers Principle should not be included within the school chemistry
curriculum, because it is not so valid in all cases. Teachers should be told to instruct students how

to treat equilibrium systems correctly with more meaningful tools, like the ones that the author
mentions in the study.
The study shows that students find chemical equilibrium very difficult, so the contents of
chemistry curriculums should be reconsidered and should be constituted by significant and valid
contents that help students to really learn and understand chemistry topics that are so abstract.
According to the study we can see that LCP is no longer so useful because there are so many cases
where application of LCP may result in inaccurate predictions that can lead students to wrong
solutions of equilibrium systems.

REFERENCES

1. Petrucci, et al. General Chemistry Principles & Modern Applications. 9th ed. Upper Saddle River,
NJ: Pearson Prentice Hall, 2007
2. Anne Marie Helmenstine, Ph.D. Law of Chemical Equilibrium Definition. Chemistry Glossary
Definition
of
Law
of
Chemical
Equilibrium.
June
18,
2014.
At:
http://chemistry.about.com/od/chemistryglossary/a/chemicaleqlawdf.htm

3. Monk, Paul (2004). Physical Chemistry: Understanding our Chemical World. Wiley.

4. Paul Kaeser, Kantonsschule Baden. Effects of Changing Conditions on the Chemical Equilibrium.
May 2010.