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Applications of Chemical Equilibrium

HEMOGLOBIN AND OXYGEN.


Hemoglobin, a protein containing iron, is the material in red blood cells responsible for
transporting oxygen to the cells. Each hemoglobin molecule attaches to four oxygen
atoms, and the equilibrium conditions of the hemoglobin-oxygen interaction can be
expressed thus: Hb (aq) + 4O 2 (g) Hb(O 2 ) 4 (aq) , where "Hb" stands for hemoglobin.
As long as there is sufficient oxygen in the air, a healthy equilibrium is maintained; but at
high altitudes, considerable changes occur.
At significant elevations above sea level, the air pressure is lowered, and thus it is more
difficult to obtain the oxygen one needs. The result, in accordance with Le Chtelier's
principle, is a shift in equilibrium to the left, away from the oxygenated hemoglobin.
Without adequate oxygen fed to the body's cells and tissues, a person tends to feel
light-headed.
When someone not physically prepared for the change is exposed to high altitudes, it
may be necessary to introduce pressurized oxygen from an oxygen tank. This shifts the
equilibrium to the right. For people born and raised at high altitudes, however, the body's
chemistry performs the equilibrium shiftby producing more hemoglobin, which also
shifts equilibrium to the right.

HEMOGLOBIN AND CARBON MONOXIDE.


When someone is exposed to carbon monoxide gas, a frightening variation on the
normal hemoglobin-oxygen interaction occurs. Carbon monoxide "fools" hemoglobin into
mistaking it for oxygen because it also bonds to hemoglobin in groups of four, and the
equilibrium expression thus becomes: Hb (aq) + 4CO (g) Hb(CO) 4 (aq). Instead of
hemoglobin, what has been produced is called carboxyhemoglobin, which is even
redder than hemoglobin. Therefore, one sign of carbon monoxide poisoning is a flushed
face.
The bonds between carbon monoxide and hemoglobin are about 300 times as strong as
those between hemoglobin and oxygen, and this means a shift in equilibrium toward the
right side of the equationthe carboxyhemoglobin side. It also means that K for the
hemoglobin-carbon monoxide reaction is much higher than for the hemoglobin-oxygen
reaction. Due to the affinity of hemoglobin for carbon monoxide, the hemoglobin puts a
priority on carbon monoxide bonds, and hemoglobin that has bonded with carbon
monoxide is no longer available to carry oxygen.

Carbon monoxide in small quantities can cause headaches and dizziness, but larger
concentrations can be fatal. To reverse the effects of the carbon monoxide, pure oxygen
must be introduced to the body. It will react with the carboxyhemoglobin to produce
properly oxygenated hemoglobin, along with carbon monoxide: Hb(CO) 4 (aq) +
4O 2 (g) Hb(O 2 ) 4 (aq) + 4CO (g). The gaseous carbon monoxide thus produced is
dissipated when the person exhales.
The NASA Computer program CEA (Chemical Equilibrium with Applications) calculates
chemical equilibrium compositions and properties of complex mixtures. Applications
include assigned thermodynamic states, theoretical rocket performance, ChapmanJouguet detonations, and shock-tube parameters for incident and reflected shocks. CEA
represents the latest in a number of computer programs that have been developed at the
NASA Lewis (now Glenn) Research Center during the last 45 years. These programs have
changed over the years to include additional techniques. Associated with the program are
independent databases with transport and thermodynamic properties of individual species.
Over 2000 species are contained in the thermodynamic database. The program is written
in ANSI standard FORTRAN by Bonnie J. McBride and Sanford Gordon. It is in wide use
by the aerodynamics and thermodynamics community, with over 2000 copies in
distribution

CEA is a program which calculates chemical equilibrium product concentrations from any
set of reactants and determines thermodynamic and transport properties for the product
mixture. Built-in applications include calculation of theoretical rocket performance,
Chapman-Jouguet detonation parameters, shock tube parameters, and combustion
properties.
Le Chteliers Principle - you discuss how Le Chteliers Principle is
supporting and in explaining the chemical equilibrium
establishments.
( if an external stress is applied to a system at equilibrium, the system will tend
to react in such way as to relieve the applied stress and tries to reestablish the
equilibrium. In chemical reaction terminology, the stress means change in
concentration, pressure, volume or temperature. Le Chateliers principle can be

understood either qualitatively or quantitatively doing some problems. However,


we restrict ourselves only to qualitative explanation)

Factors Affecting Chemical Equilibrium


Concentration, temperature and pressure effect chemical equilibrium. We explain them in detail one by one.
However, we first give you Le Chatelier's principle of equilibrium;
" If one of the factors like temperature , pressure or concentration of system is changed then system react this
change to conserve equilibrium."
1. Affect of Concentration on Equilibrium:
Adding or removing matters into reaction effect equilibrium. For example, adding reactants or removing
products increase the yield of product. On the contrary, adding products or removing reactants increase yield of
reactants. I other words, in first situation equilibrium shifts to the right and in second situation equilibrium shifts
to the left. For instance;
H2(g) + I2(g) 2HI(g)
If we add H2 gas to the container, equilibrium shifts to the right and system decrease the concentration of H2.
( Le Chatelier's principle)
2. Affect of Temperature on Equilibrium:
Heat must be given to system at equilibrium to increase temperature of it. This process gives different results in
endothermic and exothermic reactions. For example;
H2(g) + I2(g) 2HI(g) + Heat
Reaction given above is exothermic. To keep equilibrium temperature must be constant. If heat is given to
system, according to Le Chatelier's principle system wants to decrease this temperature and equilibrium shift to
the left or right. Equilibrium constant of this reaction;
Kc=[HI]2/([I2].[H2])

In an endothermic reaction; increasing temperature shift equilibrium to the right and equilibrium
constant increases.

In an endothermic reaction; increasing temperature shift equilibrium to the left and equilibrium constant
decreases.

3. Affect of Pressure on Equilibrium:


To talk about affect of pressure on equilibrium, at least one of the matters must be in gas phase. In other words,
in a reaction consisting of liquid, aqueous, or solid there is no affect of pressure on equilibrium of this system.

If one of the matters in container under constant temperature and pressure is removed or added,
pressure of the system changes. However, change in the concentration is taken into consideration not
pressure.

Temperature can be changed under constant volume. In this situation even if pressure changes, we
consider changes in the temperature while finding equilibrium constant.

In gas reactions, if there is no change in number of moles, then pressure do not effect equilibrium.

Example: Three container given below are in equilibrium with given reactions.

If volumes of them decreased from point I to II, find in which container equilibrium shifts to the right.
Solution:
I. In first container, there is no change in the number of moles. Thus, pressure does not effect this reaction.
II. In second container, there is no change in the total number of moles. But, in this reaction moles of gas in this
reaction decreases. So, equilibrium shifts to the right.
III. As you can see from the reaction, number of moles of decreases. Thus equilibrium shifts to the right.

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