Chemical Reaction Equilibria

Vinit Patil(40), Manish Pawar(41), Rehan Husain(47), Sachin Shinde(55)

Shubham Budhawant (57)

{GROUP_10}

INTRODUCTION
The chemical process industries are concerned with the transformation of raw materials into
useful products. Such transformation in most cases is achieved by means of chemical
reactions. The design and operation of reaction equipment are therefore quite an important
field in the chemical engineering profession. To be successful in this profession, the chemical
engineer should be versatile with the thermodynamics and kinetics of chemical reactions.
Thermodynamics predicts the equilibrium conversion that would be achieved in a chemical
reaction and also the effect of operating conditions on it, whereas the kinetics deals with the
rate or speed with which the desired conversion is attained in practice. Thermodynamic
analysis can also give information about the feasibility of chemical reactions. The progress
and extent of a chemical reaction are affected by changes in the reaction conditions like
temperature, pressure, composition of the reactants, etc. For example, in the synthesis of
methanol from carbon monoxide and hydrogen, the equilibrium conversion as well as the rate
of reaction are affected by changing the pressure, temperature or the relative amounts of
carbon monoxide and hydrogen in the reactant stream. The influence of these controllable
variables on the thermodynamics of reaction, or to be specific, on the equilibrium conversion,
in some situation may be in conflict with the influence of these variables on the kinetics of
the reaction. This can be illustrated by considering the effect of temperature on the oxidation
of sulphur dioxide to sulphur trioxide. The rate of this reaction increases with temperature
and from the point of view of rate alone it is better to operate the reactor at as high a
temperature as permissible. However, the equilibrium conversion to sulphur trioxide falls off
sharply with increase in temperature. The conversion is above 90% at temperatures near 800
K, but it is only 50% at 950 K. It is clear that both the kinetics (the rate) and thermodynamics
(the equilibrium) of the reaction must be considered in the choice of reaction conditions in
the commercial process for any chemical reaction. The purpose of the present chapter is to
identify the role of thermodynamics in the design and operation of chemical reaction systems.
Equilibrium conversion of a reaction sets a limit and provides a goal by which we measure
improvement in the process. It is impossible at a given set of conditions to attain a conversion
that is better than the equilibrium value calculated from thermodynamic principles. Even if
this conversion is not attainable in practice within a reasonable time, its knowledge is
valuable because it represents the best that can be expected from the reaction. It tells us
whether or not an experimental investigation of a proposed new process is worthwhile. There
is no point in trying improvement in the process by improving the rate by introducing suitable
catalysts, if thermodynamics predicts an equilibrium yield, of say, only 20% whereas a 50%
yield is necessary for the process to be economically viable. The choice of an appropriate
catalyst may give a better reaction rate, but it will not alter the equilibrium yield of the
product. The emphasis in this blog is on determining the conversion at equilibrium and on
predicting the effect of controllable variables like temperature and pressure on the
conversion. Also the industrial applications of chemical reaction equilibria.

Chemical Equilibria
In a chemical reaction, chemical equilibrium is the state in which both reactants and products
are present in concentrations which have no further tendency to change with time, so that
there is no observable change in the properties of the system.[1] Usually, this state results
when the forward reaction proceeds at the same rate as the reverse reaction. The reaction
rates of the forward and backward reactions are generally not zero, but equal. Thus, there are
no net changes in the concentrations of the reactant(s) and product(s). Such a state is known
as dynamic equilibrium.[2][3]
The concept of chemical equilibrium was developed after Berthollet (1803) found that some
chemical reactions are reversible.[4] For any reaction mixture to exist at equilibrium, the rates
of the forward and backward (reverse) reactions are equal. In the following chemical equation
with arrows pointing both ways to indicate equilibrium,[5] A and B are reactant chemical
species, S and T are product species, and α, β, σ, and τ are the stoichiometric coefficients of
the respective reactants and products:
α A + β B ⇌ σ S + τ T
The equilibrium concentration position of a reaction is said to lie "far to the right" if, at
equilibrium, nearly all the reactants are consumed. Conversely the equilibrium position is
said to be "far to the left" if hardly any product is formed from the reactants
Forward reaction rate = k + ¿ A α
Bβ ¿

Backward reaction rate = k −¿S σ

Tτ ¿

and the ratio of the rate constants is also a constant, now known as an equilibrium constant.
k +¿
K C= ¿
{S }σ {T }τ
k −¿ = ¿
{ A }α {B}β
By convention the products form the numerator. However, the law of mass action is valid
only for concerted one-step reactions that proceed through a single transition state and is not
valid in general because rate equations do not, in general, follow the stoichiometry of the
reaction as Guldberg and Waage had proposed (see, for example, nucleophilic aliphatic
substitution by SN1 or reaction of hydrogen and bromine to form hydrogen bromide).
Equality of forward and backward reaction rates, however, is a necessary condition for
chemical equilibrium, though it is not sufficient to explain why equilibrium occurs.
Despite the failure of this derivation, the equilibrium constant for a reaction is indeed a
constant, independent of the activities of the various species involved, though it does depend
on temperature as observed by the van 't Hoff equation. Adding a catalyst will affect both the
forward reaction and the reverse reaction in the same way and will not have an effect on the
equilibrium constant. The catalyst will speed up both reactions thereby increasing the speed
at which equilibrium is reached.[2][6]
Although the macroscopic equilibrium concentrations are constant in time, reactions do occur
at the molecular level. For example, in the case of acetic acid dissolved in water and forming
acetate and hydronium ions,

CH3CO2H + H2O ⇌ CH3CO−2 + H3O+

a proton may hop from one molecule of acetic acid on to a water molecule and then on to an
acetate anion to form another molecule of acetic acid and leaving the number of acetic acid
molecules unchanged. This is an example of dynamic equilibrium. Equilibria, like the rest of
thermodynamics, are statistical phenomena, averages of microscopic behaviour.

Le Chatelier's principle (1884) predicts the behaviour of an equilibrium system when changes
to its reaction conditions occur. If a dynamic equilibrium is disturbed by changing the
conditions, the position of equilibrium moves to partially reverse the change. For example,
adding more S from the outside will cause an excess of products, and the system will try to
counteract this by increasing the reverse reaction and pushing the equilibrium point backward
(though the equilibrium constant will stay the same).
If mineral acid is added to the acetic acid mixture, increasing the concentration of hydronium
ion, the amount of dissociation must decrease as the reaction is driven to the left in
accordance with this principle. This can also be deduced from the equilibrium constant
expression for the reaction:

{CH 3 CO−2 } {H 3 O+ }
K=
{CH 3 CO 2 H }

If {H3O+} increases {CH3CO2H} must increase and CH3CO−2 must decrease. The H2O is left
out, as it is the solvent and its concentration remains high and nearly constant.
A quantitative version is given by the reaction quotient.
J. W. Gibbs suggested in 1873 that equilibrium is attained when the Gibbs free energy of the
system is at its minimum value (assuming the reaction is carried out at constant temperature
and pressure). What this means is that the derivative of the Gibbs energy with respect to
reaction coordinate (a measure of the extent of reaction that has occurred, ranging from zero
for all reactants to a maximum for all products) vanishes, signalling a stationary point. This
derivative is called the reaction Gibbs energy (or energy change) and corresponds to the
difference between the chemical potentials of reactants and products at the composition of the
reaction mixture.[1] This criterion is both necessary and sufficient. If a mixture is not at
equilibrium, the liberation of the excess Gibbs energy (or Helmholtz energy at constant
volume reactions) is the "driving force" for the composition of the mixture to change until
equilibrium is reached. The equilibrium constant can be related to the standard Gibbs free
energy change for the reaction by the equation
❑❑ ∆r G−¿=−RTln K eq ¿

Where R is the universal gas constant and T the temperature.

When the reactants are in a medium of high ionic strength the quotient of activity coefficients
may be taken to be constant. In that case the concentration quotient, Kc,
 {S }σ {T }τ
K C=
{ A }α {B }β
Where [A] is the concentration of A, etc., is independent of the analytical concentration of the
reactants. For this reason, equilibrium constants for solutions are usually determined in media
of high ionic strength. Kc varies with ionic strength, temperature and pressure (or volume).
Likewise Kp for gases depends on partial pressure. These constants are easier to measure and
encountered in high-school chemistry courses.

Homogeneous and Heterogeneous Equilibria

It should be noted that the equation used above identifies a situation of homogeneous
equilibrium, in which all the substances are in the same phase or state of matter—gas, in this
case. It is also possible to achieve chemical equilibrium in a reaction involving substances in
more than one phase of matter.
Homogeneous Equilibria
In order to simplify the problems and understand the concept, we divide such reactions into
different categories, namely, the homogeneous reactions, where the components involved in
the reaction are present in the same phase and the heterogeneous reactions, where the
components involved are present in different phases. The methods of dealing with both the
reactions are different and so is the determination of the equilibrium state. In this section, we
will learn about a homogeneous equilibrium and the calculation of equilibrium constant for a
homogeneous reaction
All of the equilibria we've been talking about so far have chemical species in the same phase.
For solutions, they're all dissolved, and for gaseous equilibria, they're all gases. Equilibria in
which all species are in the same phase are called homogeneous equilibria.
Heterogeneous Equilibria
However, we can also talk about equilibria in which not all of the species are in the same
phase. These equilibria are referred to as heterogeneous equilibria. An example of a
heterogeneous equilibrium would be when an ionic compound partially dissolves in water.
To demonstrate a heterogeneous equilibrium, we'll discuss the equilibrium expression for
when calcium carbonate dissolves in water (a process known as "dissociation"). The equation
for this process is:
CaCO3(s) ⇔ Ca2+(aq) + CO32-(aq)
Let's write the equilibrium expression for this process:

Ksp = [Ca2+][CO32-]¿[CaCO3]

However, there's a twist. Recall that any time we put something in the square brackets, this
means that we need its concentration. Because CaCO3 is a solid in this process, it doesn't
really have a clearly defined concentration. As a result, we just leave it out of this expression.
(I bet you wish you could do that with everything that didn't make sense!) Likewise,
whenever you have a pure solid or a pure liquid (but not a solution) in an equilibrium
expression, you leave it out of the expression for Keq or Ksp.
Leaving the [CaCO3] term out of the Ksp expression leaves us with the following expression:
Ksp = [Ca+2] [CO3-2]
Ksp = [Ca+2][CO3-2]
The Ksp value for an ionic compound describes the degree to which the ions are present in a
saturated aqueous solution. As with other equilibria, in saturated solutions the salt will
dissolve and precipitate out at the same rates, causing no net change in ionic concentrations

The Equilibrium Constant

In 1863, Norwegian chemists Cato Maximilian Guldberg (1836-1902) and Peter Waage
(1833-1900)—who happened to be brothers-in-law—formulated what they called the law of
mass action. Today, this is called the law of chemical equilibrium, which states that the
direction taken by a reaction is dependant not merely on the mass of the various components
of the reaction, but also upon the concentration—that is, the mass present in a given volume.
This can be expressed by the formula a A + b B ⇌ c C + d D, where the capital letters
represent chemical species, and the italicized lowercase letters indicate their coefficients. The
equation [C] c [D] d / [A] a [B] b yields what is called an equilibrium constant, symbolized K.
The above formula expresses the equilibrium constant in terms of molarity, the amount of
solute in a given volume of solution, but in the case of gaseous reactants and products, the
equilibrium constant can also be expressed in terms of partial pressures. In the reaction of
water and carbon monoxide to produce hydrogen molecules and carbon dioxide (H 2 O + CO
⇋ H 2 + CO 2 ). In chemical reactions involving solids, however, the concentration of the solid
—because it is considered to be invariant—does not appear in the equilibrium constant. In the
reaction described earlier, in which calcium carbonate was in equilibrium with solid lime and
gaseous carbon dioxide, K = pressure of CO 2 .
The equilibrium constant of a chemical reaction is the value of its reaction quotient at
chemical equilibrium, a state approached by a dynamic chemical system after sufficient time
has elapsed at which its composition has no measurable tendency towards further change. For
a given set of reaction conditions, the equilibrium constant is independent of the initial
analytical concentrations of the reactant and product species in the mixture. Thus, given the
initial composition of a system, known equilibrium constant values can be used to determine
the composition of the system at equilibrium. However, reaction parameters like temperature,
solvent, and ionic strength may all influence the value of the equilibrium constant.
A knowledge of equilibrium constants is essential for the understanding of many chemical
systems, as well as biochemical processes such as oxygen transport by haemoglobin in blood
and acid-base homeostasis in the human body.
Stability constants, formation constants, binding constants, association constants and
dissociation constants are all types of equilibrium constants
For a particular reaction at a specific temperature, the ratio of concentrations between
reactants and products will always have the same value—the equilibrium constant, or K.
Because it is not dependant on the amounts of reactants and products mixed together initially,
K remains the same: the concentrations themselves may vary, but the ratios between the
concentrations in a given situation do not.

Le Chatelier's Principle
Not all situations of equilibrium are alike: depending on certain factors, the position of
equilibrium may favour one side of the equation or the other. If a company is producing
chemicals for sale, for example, its production managers will attempt to influence reactions in
such a way as to favour the forward reaction. In such a situation, it is said that the equilibrium
position has been shifted to the right. In terms of physical equilibrium, mentioned above, this
would be analogous to what would happen if you were holding your arms out on either side
of your body, with a heavy lead weight in your left hand and a much smaller weight in the
right hand.
Your center of gravity, or equilibrium position, would shift to the left to account for the
greater force exerted by the heavier weight.
A value of K significantly above 1 causes a shift to the right, meaning that at equilibrium,
there will be more products than reactants. This is a situation favourable to a chemical
company's managers, who desire to create more of the product from less of the reactants.
However, nature abhors an imbalance, as expressed in Le Chatelier's principle. Named after
French chemist Henri Le Chatelier's (1850-1936), this principle maintains that whenever a
stress or change is imposed on a chemical system in equilibrium, the system will adjust the
amounts of the various substances to reduce the impact of that stress.
Suppose we add more of a particular substance to increase the rate of the forward reaction. In
an equation for this reaction, the equilibrium symbol is altered, with a longer arrow pointing
to the right to indicate that the forward reaction is favored. Again, the equilibrium position
has shifted to the right—just as one makes physical adjustments to account for an imbalanced
weight. The system responds by working to consume more of the reactant, thus adjusting to
the stress that was placed on it by the addition of more of that substance. By the same token,
if we were to remove a particular reactant or product, the system would shift in the direction
of the detached component.
Note that Le Chatelier's principle is mathematically related to the equilibrium constant.
Suppose we have a basic equilibrium equation of A + B ⇌ C, with A and B each having
molarities of 1, and C a molarity of 4. This tells us that K is equal to the molarity of C divided
by that of A multiplied by B = 4/(1 · 1). Suppose, now, that enough of C were added to bring
its concentration up to 6. This would mean that the system was no longer at equilibrium,
because C/(A · B) no longer equals 4. In order to return the ratio to 4, the numerator (C) must
be decreased, while the denominator (A · B) is increased. The reaction thus shifts from right
to left.
General statement of Le Chatelier's principle
Le Chatelier's principle refers to states of thermodynamic equilibrium. The latter are stable
against perturbations that satisfy certain criteria; this is essential to the definition of
thermodynamic equilibrium.
For this, a state of thermodynamic equilibrium is most conveniently described through a
fundamental relation that specifies a cardinal function of state, of the energy kind, or of the
entropy kind, as a function of state variables chosen to fit the thermodynamic operations
through which a perturbation is to be applied.[7][8][9]
In theory, and, nearly, in some practical scenarios, a body can be in a stationary state with
zero macroscopic flows and rates of chemical reaction (for example, when no suitable
catalyst is present), yet not in thermodynamic equilibrium, because it is metastable or
unstable; then Le Chatelier's principle does not necessarily apply.
Effect of 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 partly 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.
This can be illustrated by the equilibrium of carbon monoxide and hydrogen gas, reacting to
form methanol.
CO + 2 H2 ⇌ CH3OH
Suppose we were to increase the concentration of CO in the system. Using Le Chatelier's
principle, we can predict that the amount of methanol will increase, decreasing the total
change in CO. If we are to add a species to the overall reaction, the reaction will favour the
side opposing the addition of the species. Likewise, the subtraction of a species would cause
the reaction to "fill the gap" and favour the side where the species was reduced. This
observation is supported by the collision theory. As the concentration of CO is increased, the
frequency of successful collisions of that reactant would increase also, allowing for an
increase in forward reaction, and generation of the product. Even if the desired product is not
thermodynamically favored, the end-product can be obtained if it is continuously removed
from the solution.
The effect of a change in concentration is often exploited synthetically for condensation
reactions (i.e., reactions that extrude water) that are equilibrium processes (e.g., formation of
an ester from carboxylic acid and alcohol or an imine from an amine and aldehyde). This can
be achieved by physically sequestering water, by adding desiccants like anhydrous
magnesium sulfate or molecular sieves, or by continuous removal of water by distillation,
often facilitated by a Dean-Stark apparatus.

Effect of change in temperature

The effect of changing the temperature in the equilibrium can be made clear by 1)
incorporating heat as either a reactant or a product, and 2) assuming that an increase in
temperature increases the heat content of a system. When the reaction is exothermic (ΔH is
negative, puts energy out), heat is included as a product, and, when the reaction is
endothermic (ΔH 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.
Take, for example, the reversible reaction of nitrogen gas with hydrogen gas to form
ammonia:
N2(g) + 3 H2(g) ⇌ 2 NH3(g)    ΔH = -92 kJ mol−1
Because this reaction is exothermic, it produces heat:
N2(g) + 3 H2(g) ⇌ 2 NH3(g) + heat
If the temperature were increased, the heat content of the system would increase, so the
system would consume some of that heat by shifting the equilibrium to the left, thereby
producing less ammonia. More ammonia would be produced if the reaction were run at a
lower temperature, but a lower temperature also lowers the rate of the process, so, in practice
(the Haber process) the temperature is set at a compromise value that allows ammonia to be
made at a reasonable rate with an equilibrium concentration that is not too unfavourable.
In exothermic reactions, increase in temperature decreases the equilibrium constant, K,
whereas, in endothermic reactions, increase in temperature increases the K value.
Le Chatelier's principle applied to changes in concentration or pressure can be understood by
having K have a constant value. The effect of temperature on equilibria, however, involves a
change in the equilibrium constant. The dependence of K on temperature is determined by
the sign of ΔH. The theoretical basis of this dependence is given by the Van 't Hoff equation.
Effect of change in pressure
The equilibrium concentrations of the products and reactants do not directly depend on the
total pressure of the system. They may depend on the partial pressures of the products and
reactants, but if the number of moles of gaseous reactants is equal to the number of moles of
gaseous products, pressure has no effect on equilibrium.
Changing total pressure by adding an inert gas at constant volume does not affect the
equilibrium concentrations (see Effect of adding an inert gas below).
Changing total pressure by changing the volume of the system changes the partial pressures
of the products and reactants and can affect the equilibrium concentrations (see Effect of
change in volume below).
Effect of change in volume
Changing the volume of the system changes the partial pressures of the products and
reactants and can affect the equilibrium concentrations. With a pressure increase due to a
decrease in volume, the side of the equilibrium with fewer moles is more favourable [4] and
with a pressure decrease due to an increase in volume, the side with more moles is more
favourable. There is no effect on a reaction where the number of moles of gas is the same on
each side of the chemical equation.
Considering the reaction of nitrogen gas with hydrogen gas to form ammonia:
N2 + 3 H24 moles ⇌ 2 NH32 moles    ΔH = -92kJ mol−1
Note the number of moles of gas on the left-hand side and the number of moles of gas on the
right-hand side. When the volume of the system is changed, the partial pressures of the gases
change. If we were to decrease pressure by increasing volume, the equilibrium of the above
reaction will shift to the left, because the reactant side has a greater number of moles than
does the product side. The system tries to counteract the decrease in partial pressure of gas
molecules by shifting to the side that exerts greater pressure. Similarly, if we were to increase
pressure by decreasing volume, the equilibrium shifts to the right, counteracting the pressure
increase by shifting to the side with fewer moles of gas that exert less pressure. If the volume
is increased because there are more moles of gas on the reactant side, this change is more
significant in the denominator of the equilibrium constant expression, causing a shift in
equilibrium.
Effect of a catalyst
A catalyst increases the rate of a reaction without being consumed in the reaction. The use of
a catalyst does not affect the position and composition of the equilibrium of a reaction,
because both the forward and backward reactions are sped up by the same factor.
For example, consider the Haber process for the synthesis of ammonia (NH3):
N2 + 3 H2 ⇌ 2 NH3
In the above reaction, iron (Fe) and molybdenum (Mo) will function as catalysts if present.
They will accelerate any reactions, but they do not affect the state of the equilibrium.

Application of chemical equilibiria

The main application of Chemical Equilibria in industrial process is to maximise the desired
product concentration by minimising the leftover reactants.
Lime production from Limestone
An application of a chemical equilibrium for an industrial system is lime production from
limestone.  The products which are made from burnt limestone are called lime (i.e. quicklime
and hydrated lime).  Limestone is naturally occurring, and it also consist of minerals in small
pieces.  Presently, limestone products are used as a crucial part in most industrial processes.
At first, it is mined, as it is used  for many applications, such as pH adjustment, (water
treatment) product filter (asphalt, ready mix concrete) raw material in the production of glass,
pulp & paper, cement and steel, fuel gas desulfurization and stone blocks production   There
are very few environmental effects of calcium oxide and calcium hydroxide when it is
properly used. The high pH of 12.45 is reduced to a pH in the range between 7.5 and 8.5 in a
natural manner.  There are quite a few normal precautions that the workers working with
chemicals must take.  Some of the hazards consist of: the high temperatures of calcium oxide,
irritation to the eyes and lungs from lime dust, as well as many more.  Some of the
environmental impacts this system has on society are: air emissions, energy consumption and
fuels, waste water solid waste generation and noise.  The reactions which consist of lime help
to improve the hydrated lime contamination effects.
The chemical equation governing this process is:

calcium carbonate (limestone) <–> calcium oxide (lime) + carbon dioxide

CaCO3(s) <–> CaO(s) + CO2(g) (ΔH = +178 kJ mol-1)

Since the solids in this chemical equation have a concentration which is constant, the
only equilibrium expression which can satisfy this system is: Kp = pCO2 atm or Pa.  Since the
forward reaction is endothermic, 178kJ of heat energy is absorbed for every mole of calcium
oxide being formed: CaO is formed at a high temperature.  Since one mole of gas is formed,
there is a net increase in the moles of gas in the process of lime production, since there are
no gaseous products.  Decreasing the pressure will allow more gas molecules to be formed if
possible, meaning more carbon dioxide is able to be formed (more lime). This reaction occurs
in a ventilated lime kiln at a normal atmospheric pressure. As the products are removed,
the forward reaction is favored, which increases the concentration of the products.  An
example is, by burning lime stone; CO2 is continuously removed from the kiln to shift the
reaction in the forward direction.  By continuously removing one of the products, it maintains
Qc at a value less than Kc, and so keeps the reaction moving in the forward direction.
Outside forces affecting this system would be how nature affects limestone caves: the ground
has limestone within it, and as the acidic rain reaches the earth, an acid/base reaction occurs:
(acidic rain: CO2 + H2O ↔ H2CO3 ).This rain will behave as an acid in the limestone
formation process: dissolves the limestone.  (H2CO3 (g) + CaCO3 (s) ↔ 2HCO3– (aq) +
Ca2+ (s):  CO32- acts as a base).  In this process, the equilibrium is constantly moving in
nature, and this becomes evident with the formation of stalagmites and stalactites within these
caves. The impact of this system on society is known to be good, as it is related to the
chemical equation being favored in moving in the forward reaction only, which allows more
production of lime to occur.

In this reaction scheme the solid concentration is constant yielding equilibrium as

The reaction scheme is endothermic as it absorbs 178 kJ of heat in the form of energy for
conversion to the desired product of CaO whose formation is influenced by high temperature
making the reaction scheme feasible till it reaches the temperature of denoting the reaction
scheme to be always favoured on the right hand side.

In addition, the gaseous carbon di-oxide is evolved from the reaction since there is no trace of
gaseous reactant and hence the lowering of pressure favours the formation of more product.
When compared to old kilns, modern rotary kiln favours high production rate of lime by
continuous extraction of lime from the process

Methanol Production

Chemical equilibrium, it is simply defined as a reaction occurring at equal rates in its forward
and reverse directions, so that the concentrations of the reacting substances do not change
with time. It describes the characteristic of maintaining a balance of reactions, and can be
applied to varying mediums, many of which are chemical reactions. One such example of
chemical equilibrium that is representative in real life is the production of methanol through
the combination of both Hydrogen atoms and Carbon Monoxide molecules.

The synthesis reaction can be represented by the equation:

CO(g) + 2 H2(g) ↔ CH3OH(g)

Were all species are in a gaseous state

In the synthesis of methanol, large amounts of hydrogen and carbon monoxide are combined
at high temperatures and pressures to create the product of methanol. It
is immediately noticeable that the equation confers to a homogeneous equilibrium where all
species are in the same state. It can also be noted that this reaction is quite simple when
compared to Le Chatelier’s Principles. For example there are 3 methods of disturbing this
system at equilibrium:

Changing Concentration:
When a certain concentration is increased or decreased, the rate of change will remain
constant but the overall equilibrium will be shifted in the corresponding direction,

CO(g) + 2 H2(g) ↔ CH3OH(g)

(When the concentrations of reactants are increased, the equilibrium shifts right

to accommodate for the change and creates more products, in relation if the concentration of
the reactants is decreased the equilibrium will shift left to utilize less reactants)
Inversely……

(When the concentrations of products are increased, the equilibrium shifts left to
accommodate for the change and utilizes more reactants, in relation if the concentration of
the products is decreased the equilibrium will shift right to create more products)

Changing Temperature:
Temperature has a major role in the production of Methanol, through the combination of
Hydrogen and Carbon Monoxide, the synthesis itself can only occur when high heat and
pressure are present. But with varying levels of temperature the concentrations of either the
reactants or products can change. For example:

CO(g) + 2 H2(g) + HEAT ↔ CH3OH(g)

or…..

CO(g) + 2 H2(g) ↔ CH3OH(g)+ HEAT

When heat is added to the reaction, the equilibrium shifts right and more product is produced
as a result, in relation when temperature is decreased, the equilibrium shifts left and more
reactant is created.

Changing Pressure:
Pressure also has an important role on the equilibrium of this equation, pressure is constantly
measured and adjusted so that the equilibrium will be optimized to produce the most
product. But with varying levels of pressure the concentrations of either the reactants or
products can change. For example:

CO(g) + 2 H2(g) ↔ CH3OH(g)

If the pressure is increased the equilibrium will shift to the right, the side with the fewest
moles and create more product, while if there was a decrease in pressure the equilibrium
would shift left, to the side with the most moles, creating more reactants.
Now that the main factors affecting the equilibrium are known, the reasons behind why such
a disturbance would occur can be explained. Throughout the synthesis of methanol, many
safety precautions must be adhered many of which include safe operating temperatures and
pressures. This is important to note because it allows for technicians to both optimize (in this
case increase) both the temperature and pressure to help shift the equilibrium and as a result
produce the most product (Methanol) in the safest environment. The maximum temperature
allowed during the synthesis is roughly 400 degrees Celsius, while the maximum pressure
allowed is around 300 ATM. this is helpful in many ways, since the reaction is optimized a
large sum of product will be created which will continue to supply the demand for it.

The reaction parameters for producing methanol are achieved by maintaining temperature at
by using the catalysts of  by maintaining reactor pressure at 5 MPa to 10 MPa. In the reaction
scheme, 3 moles of synthesis gas is required for making one mole of methanol vapour which
is further condensed to liquid state via condensing process. By Le-Chatelier’s principle, the
high-pressure maintenance is the main parameter for the formation of the products and the
inclusion of smaller amount of catalyst with moderate temperature maintenance favours the
product formation of methanol. The kinetic expression based on pressure for the reaction
scheme is,

Haber process

The Haber process was founded by two German chemists, Fritz Haber and Carl

Bosch. Fritz Haber was responsible for discovering the important ingredients to form
ammonia gas (NH3 (g)). Carl Bosch had discovered the relationship between high pressures
on chemical reactions. The Haber process is a process where nitrogen gas (N2 (g)) and
hydrogen gas (H2 (g)) are combined to form ammonia gas (NH3 (g)) through an exothermic
reaction which means it because it releases energy (ΔH = −92.4 kJ/mol).

Reaction:
                                N2 (g) + 3H2 (g) ↔ 2NH3 (g) + heat

The equilibrium expression for this reaction is:

Keq = [NH3]^2 / [N2] [H2]^3

Le Chatelier's Principle and relation to equilibrium:

The Haber process associates the Le Chatelier's Principle and is also related to equilibrium.

Reaction:
  N2 (g) + 3H2 (g) ↔ 2NH3 (g) + heat
Increase in H2 – equilibrium shifts to right
Decrease in NH3 – equilibrium shifts to right
Increase in Heat – equilibrium shifts to right
Pressure:
 An increase in pressure will produce a high yield of ammonia while shifting the
reaction to the right.
 When the pressure of the system is increased, the system will move to the right
because there are more molecules on the left side than on the right, this will ensure a
decrease in the overall pressure of the system.
 In order to get the maximum amount of ammonia possible, highest possible pressure
is needed, 200 atm is a high pressure.

Temperature:
 A decrease in temperature will produce a high yield of ammonia while shifting the
reaction to the right.
 A drop in temperature will cause the reaction to go right because the reaction is
exothermic and heat is being released. This means that 400 – 450°C is the temperature
that will produce a high yield of ammonia while the time is short.
 The system will have to adjust itself to counteract the change and make up for the
energy that it has lost. When more energy is being made there is more ammonia being
made. Decreasing the temperature will produce a higher amount of ammonia yield cause
the reaction to be slower while as if the temperature was to be increased and sped up it
would produce a lower amount of ammonia yield.

Concentration:
If you increase the concentration of nitrogen gas (N2 (g)) and (H2 (g)) which are the reactants
it will increase the concentration of NH3 which is the product, it will allow the equilibrium to
shift to the right and counteract the change and a high amount of ammonia yield will be
produced.

Catalyst:
A catalyst is used to speed the reaction up, it does not participate in the reaction itself and has
no effect on the concentrations of the reaction. The catalyst used in this reaction of N2 gas
and H2 gas to produce ammonia NH3 is an Iron Catalyst, it will speed the reaction up so
ammonia can be produced more quickly at a low temperature. The catalyst is very helpful in
terms of costs and time.

Uses:
Ammonia is used to make fertilizers. Fertilizers are used in the fields to grow crops such as
corn, sunflower and soybeans.

Also there is a production of:

 Ammonium sulphate, (NH4)2SO4

 Ammonium phosphate, (NH4)3PO4
 Ammonium nitrate, NH4NO3
Lastly, another use of ammonia was during World War I where nitric acid was produced
using the Haber process:
 Nitric acid, HNO3

References:

1. ^ Jump up to: a b c Atkins, Peter; De Paula, Julio (2006). Atkins' Physical Chemistry (8th
ed.). W. H. Freeman. pp. 200–202. ISBN  0-7167-8759-8.
2. ^ Jump up to: a b Atkins, Peter W.; Jones, Loretta (2008). Chemical Principles: The Quest
for Insight (2nd ed.). ISBN 978-0-7167-9903-0.
3. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997).
Online corrected version:  (2006–) "chemical equilibrium".
doi:10.1351/goldbook.C01023
4. ^ Berthollet, C.L. (1803). Essai de statique chimique
5. ^ The notation ⇌ was proposed in 1884 by the Dutch chemist Jacobus Henricus van’t
Hoff. See: van’t Hoff, J.H. (1884). Études de Dynamique Chemique
6. ^ Brady, James E. (2004-02-04). Chemistry: Matter and Its Changes (4th ed.). Fred
Senese. ISBN 0-471-21517-1.
7. ^ Münster, A. (1970), pp. 173–174.
8. ^ Callen, H.B. (1960/1985), Chapter 8, pp. 203–214.
9. ^ Bailyn, M. (1994), Chapter 8, Part A, pp. 312–319.
10. ^ Jump up to: a b Atkins (1993), p. 114
11. P. W. Atkins, Physical Chemistry, 7th Ed.(2002) Oxford University Press, New York.