Dynamic equilibria

Sunday, February 4, 2024 9:26 PM

Reversible and irreversible reactions

Reactions that have little to or no any reactants remaining at the end of the reaction mixed with the products and releasing high
amounts of heat energy to the surrounding as the reaction occurs (exothermic) having large ΔH negative values are said to be
irreversible reactions

Reactions that have noticeable to high amounts of reactants remaining at the end of the reaction mixed with the products and
releasing small amounts of heat energy to the surrounding as the reaction occurs (exothermic) having small ΔH negative values
are said to be reversible reactions

Deciding on if a reaction is reversible or not

In reversible reactions the reactants gets together to form products and the products breaks down again back to the reactants.
In order for the reaction to be a reversible reaction both backward and forward reactions should occur up to a significant
noticeable extent. A reaction is not reversible if both forward and backward reactions does not occur or that both backward and
forward reactions still might occur but the backward reaction does not occur up to a noticeable extent meaning that if the
forward reaction occurs / completes up to 99% or more and that backward reaction occurs only up to 1% or less then the
reaction is not reversible as backward reaction is so small that it is negligible.

Ex ; -
Water molecules ionizes to form OH- and H+ ions (forward reaction). Out of these ionized ions a small amount of OH- and H+
ions reacts with each other to reform water molecules (backward reaction) due to slight electrical conductivity of water. This
backward reaction occurs in about 1 in 150 million water molecules. So here forward reaction occurs approximately up to 99%
so not reversible reaction.

When hydrogen and iodine left in a close container at 573k about 90% of the hydrogen and the iodine reacts to form hydrogen
iodide while 10% of hydrogen and iodine remains in the final mixture. This is because about 10% of the formed hydrogen iodide
decomposes slowly to breakdown back into the reactants of hydrogen and iodine. When the concentration of the products and
the reactants remains same the reaction is said to be in equilibrium state. The reversible reaction is represented by ⇌ to show
both the forward and the backward reactions.

H2 + I2 ⇌ 2HI

Establishment of the equilibrium

For hydrogen and iodine forming hydrogen iodide in a reversible reaction overtime the concentration of the formed hydrogen
iodide decreases showing that the rate of the forward reaction decreases and that the concentration of the hydrogen and
iodine increases showing that the rate of the backward reaction increase as instantly once hydrogen iodide is produced it is
decomposed. When it comes to the point where there is no further change in concentration of the reactants and products and
that the rate of the backward and the forward reactions becomes equal it is in dynamic equilibrium. Dynamic equilibrium is said
as both forward and backward reactions takes place at the same rate and that these is no change in concentrations of the
reactants and the products.

Conditions for equilibrium:

- Reaction must be in a closed system
- Reaction must be reversible

Features of equilibrium:
- Rate of forward and backward reactions same
- Forward and backward reactions continuously
occurring
- Concentration of reactants and product remains
constant

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 occurring
- Concentration of reactants and product remains
constant

Changing composition of an equilibrium mixture

The composition is the concentration of each component in the mixture. If mixture in equilibrium the composition of each
component remains constant over time. But if we change one of the conditions (ex - add or remove components or change the
temperature ) this will alter the concentration of the components so the composition of the components changes. This change
in composition is referred to as the change in position of the equilibrium. Change in composition will cause the concentration of
one component to decrease and other to increase. The equilibrium position shifts to the direction of the component in which
the concertation increases. So a change in conditions causes for the equilibrium position to either shift left or right or not
change.

Ex ;-
Addition of acid to a yellow solution containing chromate (vi) ions causes for the solution to change color from yellow to orange
as dichromate (vi) ions are produced and concentration increases.

CrO42- + H+ -> Cr2O72- + H2O

Here if we add acid the solution changes color from yellow to orange as the concentration of H+ increases leading to an increase
of Cr2O72- than the concentration of CrO42 so the equilibrium position has moved to right. If we add enough sufficient alkali the
concentration of OH- ions will increase than the H+ ions leading to an increase in concentration of CrO42- than the
concentration of the Cr2O72- so causes for the color change to shift from the orange color to yellow color so the equilibrium
position shifts to left.

Factors affecting equilibrium position

- Concentration
- Pressure
- Catalyst
- Temperature

Concentration
An increase in concentration of one of the reactants causes for the rate of the forward reaction to increase. This leads to more
products being formed as backward reaction rate also increases to establish a new equilibrium. So as backward reaction rate
increased more products formed in the new established equilibrium that that of the concentration of the products of the
previously established equilibrium. So as the concentration of the products greater in the newer equilibrium that that of the
older equilibrium the equilibrium position has switched right.

Pressure
Can only be applied for reversible reactions involving gasses. The pressure can be altered by changing the volume of the sample.
Greater the volume lower the pressure while lower the volume greater the pressure. Th change in pressure can be done by
changing the number of reactant or product molecules with in the given volume. In order to increase the pressure the number
of moles of reactants or product molecules should be increased with in the fixed volume. In order to decrease the pressure the
number of moles or reactants or products should be decreased with in the same fixed volume. This change in pressure by
altering the volume can be achieved by pulling out or pushing in the plunger of the syringe.

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So conclusion made that the equilibrium position shifts to lower side.

Ex; -

N2 + 3H2 ⇌ 2NH3
Here balanced equation shows that reactant gas has a total of 4 mols while the product gaseous sample has only 2 mols. So
here the reactants has greater pressure as its pressure has been increased by greater number of moles with in a fixed same
volume. So this increases the rate of forward reaction. The rate of backward reaction also increases and becomes equal to the
rate of the forward reaction to establish a new equilibrium. So now more products are being produced in the newly established
equilibrium than that of the old equilibrium. So the position of the equilibrium has switched to the right. So more ammonia
produced once the number of moles of reactants increased leading to increase in pressure of the reactants.

Temperature
Change in temperature changes the rate of both forward and backward reaction. An increase in temperature increases the rate
of the forward reaction and the backward reaction. However the rate of increase of the endothermic reaction is greater than
that of the exothermic reaction. So increase in temperature shifts the position of equilibrium to the direction of the
endothermic reaction.

So an increase in temperature causes for temperature of the endothermic reaction to increase greater than that of the
exothermic reaction. So the position of equilibrium shifts to the direction of the endothermic reaction. The decrease in
temperature causes for the rate of endothermic reaction to decrease lower than the rate of exothermic reaction. So position of
equilibrium shifts to the exothermic reaction direction.

Catalyst
Rate of both forward and backward reactions increases together. This increase is same for both forward and backward reaction.
So the position of equilibrium not altered so remains same. It only reduces the time it takes for the reaction mixture to establish
the equilibrium.

Qualitative predictions and their limitations

Statements made about the change in the position of the equilibrium are just predictions. Sometimes it's impossible to predict
as there are more than one conditions changed leading to effect on the equilibrium position. In these situations we cannot
determine which change in condition has the greatest effect.

Ex ; -
Under heat brown nitrogen dioxide can decompose to N2O4 which is colorless and that the N2O4 will decompose to give NO2

2NO2 ⇌ N2O4

The reactant gasses put in a closed container and put in a hot water bath at room temperature. The forward reaction is

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The reactant gasses put in a closed container and put in a hot water bath at room temperature. The forward reaction is
exothermic. The temperature and the pressure both rises. Increase in temperature we predict that the position of equilibrium
shifts to left while increase in pressure we predict that position of equilibrium shifts to right. We cannot exactly know which
change in condition has greater effect.

Kinetics and reversibility to industrial processes

These can be used to design and conditions for many industrial processes to maximize profit. Problems faced in converting
reactants to products are of how fast they can be converted as quickly as possible (kinetics) and complete as possible without
undergoing reversible reactions (reversibility).

Haber process
Process of manufacture of ammonia by direct synthesis of nitrogen and hydrogen.

N2 + 3H2 ⇌ 2NH3

Higher the pressure greater the yield but higher the energy cost. But lower the pressure lower the cost but lower the yield. So
as compensation for these factors pressure of 250 atms used.

To increase the efficiency the unreacted hydrogen and nitrogen molecules pumped into the reaction chamber to be mixed with
the new fresh hydrogen and nitrogen molecules to react.

The contact process

Used to manufacture sulfuric acid (H2SO4). It involves a heterogenous solid catalyst vanadium (v) oxide which catalyzes
formation of the sulfur trioxide from sulfur trioxide and oxygen which gives it the name.

SO2 + 1/2O2 ⇌ SO3

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