Module 1

Chemical thermodynamics and kinetics

1st law
The first law of thermodynamics, also known as Law of Conservation of Energy,
states that energy can neither be created nor destroyed; energy can only be
transferred or changed from one form to another. For example, turning on a light
would seem to produce energy; however, it is electrical energy that is converted.

A way of expressing the first law of thermodynamics is that any change in the
internal energy (∆E) of a system is given by the sum of the heat (q) that flows across
its boundaries and the work (w) done on the system by the surroundings:

ΔE=q+wΔE=q+w

This law says that there are two kinds of processes, heat and work, that can lead to
a change in the internal energy of a system. Since both heat and work can be
measured and quantified, this is the same as saying that any change in the energy of
a system must result in a corresponding change in the energy of the surroundings
outside the system. In other words, energy cannot be created or destroyed. If heat
flows into a system or the surroundings do work on it, the internal energy increases
and the sign of q and w are positive. Conversely, heat flow out of the system or work
done by the system (on the surroundings) will be at the expense of the internal
energy, and q and w will therefore be negative.

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2nd LAW
The second law of thermodynamics says that the entropy of any isolated system
always increases. Isolated systems spontaneously evolve towards thermal
equilibrium—the state of maximum entropy of the system. More simply put: the
entropy of the universe (the ultimate isolated system) only increases and never
decreases.

A simple way to think of the second law of thermodynamics is that a room, if not
cleaned and tidied, will invariably become messier and more disorderly with time –
regardless of how careful one is to keep it clean. When the room is cleaned, its
entropy decreases, but the effort to clean it has resulted in an increase in entropy
outside the room that exceeds the entropy lost.

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3rd LAW
The third law of thermodynamics states that the entropy of a system approaches a
constant value as the temperature approaches absolute zero. The entropy of a
system at absolute zero is typically zero, and in all cases is determined only by the
number of different ground states it has. Specifically, the entropy of a pure crystalline
substance (perfect order) at absolute zero temperature is zero. This statement holds
true if the perfect crystal has only one state with minimum energy.
https://www.youtube.com/watch?v=kswiDQ2aAKA

ENTROPY THEORY
Entropy is the measure of disorder or randomness. This randomness could be in
regards to the entire universe or a simple chemical reaction or something as simple
as the heat exchange and heat transfer. The term disorder denotes the irregularity or
lack of uniformity of a thermodynamic system.

The entropy is denoted by ‘S’ and it is an extensive property because the value of
entropy or entropy change is dependent on the substance present in a thermodynamic
system. Entropy is an interesting concept as it challenges the belief of complete heat
transfer. It helps redefine the second law of thermodynamics.

Entropy relates to spontaneity i.e.; the more is the spontaneity in a thermodynamic

process, the higher is its entropy or the degree of disorder. In simpler words, entropy
gives us an idea about that portion of energy that does not convert into work done and
adds to the disorder of the system instead. Since energy gives the ability to get work
done, it is practically impossible for all the energy to be used in doing work. Entropy
gives us a measure of that.

As is clear from the law of thermodynamics that energy can neither be created nor
destroyed but can be converted from one form to another, it is not possible to signify
entropy at a single point, and hence, it can be measured as a change. That is why we
calculate the entropy change.

Entropy Change
Entropy change can be defined as the change in the state of disorder of a
thermodynamic system that is associated with the conversion of heat or enthalpy into
work. A system with a great degree of disorderliness has more entropy.
Entropy is a factor of state function i.e., its value does not dependent on the pathway
of the thermodynamic process and it acts as the determinant of only the initial and final
state of the system. In the rule of chemical reactions, the changes in entropy occur as
a result of the rearrangement of atoms and molecules that change the initial order of
the system. This may either lead to an increase or a decrease in the randomness of
the system and hence, will lead to an increase or a decrease in the entropy
respectively.

Change in Entropy Formula Thermodynamics

The entropy change of a thermodynamic system is represented as ΔS. We can
calculate the entropy change of a chemical reaction or a system by using the change
in entropy formula:
ΔS=(Q/T)rev
Where,
Q is the heat transfer to or from the thermodynamic system
T is the absolute temperature.
The SI unit of entropy change is J/Kmol

PRACTICE QUESTIONS ON ENTROPY: https://www.youtube.com/watch?v=Bdn3u2OHvKE

SPONTANITY OF A CHEMICAL REACTION AND

GIBBS FREE ENERGY
Gibbs equation helps us to predict the spontaneity of reaction on the basis of
enthalpy and entropy values directly. When the reaction is exothermic, enthalpy of
the system is negative making Gibbs free energy negative. Hence, we can say that
all exothermic reactions are spontaneous.
In the case of endothermic reactions, when enthalpy of the system is positive, the
process is spontaneous under two conditions:

• Temperature is very high to make the Gibbs energy value negative

• Entropy change is very high to make the Gibbs free energy negative.
Spontaneity can only indicate if a reaction can occur not necessarily if a reaction will
occur. For example, the conversion of diamond to graphite is a spontaneous process
at Standard Temperature and Pressure (STP) but it is a slow process. It will take
years for the transformation to occur.
The energetics of processes for systems at constant temperature and pressure, the
appropriate quantity is known as the Gibbs free energy. The Gibbs free energy has a
very useful property; it decreases for a spontaneous process at constant
temperature and pressure. Under such conditions the decrease in Gibbs free energy
equals the maximum amount of energy available for work, whereas if it increases for
some transition, the change in Gibbs free energy represents the minimum amount of
work required.
The transformation of a system from one state to another, at constant temperature
and pressure, is spontaneous if the Gibbs free energy decreases. If the Gibbs free
energy is unchanged by the transformation the two states are in equilibrium. In other
words the criterion for the thermodynamic equilibrium of a system at constant
temperature and pressure is that the Gibbs free energy of the system be at the
minimum value. The Gibbs free energy is sometimes called the thermodynamic
potential at constant pressure in order to indicate its analogy with the potential
energy of a mechanical system, which also has a minimum value under equilibrium
conditions.
General expression for Gibbs energy change at constant temperature is expressed
as:
△Gsys△Gsys = △Hsys–T△Ssys△Hsys–T△Ssys
Where,
△Gsys△Gsys = Gibbs energy change of the system

△Hsys△Hsys = enthalpy change of the system

△Ssys△Ssys = entropy change of the system

TT = Temperature of the system

Above equation is popularly known as Gibbs equation. Gibbs’ equation relates
enthalpy and entropy of the system. We know that for a spontaneous process, the
total entropy change, △Stotal△Stotal is greater than zero.

△Stotal△Stotal = △Ssys+△Ssurr△Ssys+△Ssurr

Where,

△Stotal△Stotal = total entropy change for the process

△Ssys△Ssys = entropy change of the system

△Ssurr△Ssurr = entropy change of the surrounding

In case of thermal equilibrium between system and surrounding, temperature change

between system and surrounding, △T△T = 00. Hence, we can say that enthalpy lost
by the system is gained by the surrounding. Hence, the entropy change of the
surrounding is given as,
△Ssurr△Ssurr = △HsurrT=–△HsysT△HsurrT=–△HsysT
△Stotal△Stotal = △Ssys+(−△HsysT) △Ssys+(−△HsysT)

△Hsurr△Hsurr = change in enthalpy of the surrounding

△Hsys△Hsys = change in enthalpy of the system

As discussed earlier, for the spontaneity of a process, ΔStotal > 0. Above equation
becomes,

T△Ssys–△Hsys>0T△Ssys–△Hsys>0

△Hsys–T△Ssys<0△Hsys–T△Ssys<0
Above equation can be related to Gibb’s equation as,
△Gsys<0 △Gsys<0

On the basis of above equation, we can infer:

• △Gsys<0△Gsys<0, the process is spontaneous

• △Gsys>0△Gsys>0,, the process is non-spontaneous

CONCEPT OF ACTIVATION ENERGY AND ENERGY

BARRIER
Activation energy is defined as the minimum amount of extra energy required by a
reacting molecule to get converted into product. It can also be described as the
minimum amount of energy needed to activate or energize molecules or atoms so
that they can undergo a chemical reaction or transformation.
Activation energy is denoted by Ea. It is usually measured in joules (J) and or
kilojoules per mole (kJ/mol) or kilocalories per mole (kcal/mol).

1. Nature of Reactants
In the case of ionic reactant, the value of (Ea) will be low because there is an
attraction between reacting species. While in the case of covalent reactant the value
of Ea will be high because energy is required to break the older bonds.
2. Effect of Catalyst
Positive catalyst provides such an alternate path in which the value of Ea will be low,
while the negative catalyst provides such an alternate path in which the value of
Ea will be high.
Note: Activation energy does not depend upon the temperature, pressure, volume,
concentration, or coefficients of reactant.

Exothermic Reaction

Activation energy for Forward reaction (Ea)f

Activation energy for Forward reaction (Ea)b
(Ea)f < (Ea)b
(ROR)f > (ROR)b
△H = (Ea)f – (Ea)b
△H = -ve value
(Ea)f = △H Only one can be possible for Exothermic Reaction
(Ea)f > △H
(Ea)f < △H
Endothermic Reaction
(Ea)f > (Ea)b
(ROR)f < (ROR)b
△H = (Ea)b – (Ea)f
△H = +ve value
(Ea)f > △H (Always )…………universal

PLEASE REFER TO: https://www.youtube.com/watch?v=YacsIU97OFc

ARRHENIUS EQUATION

Image Source: https://www.sciencedirect.com/topics/engineering/arrhenius-

equation

EFFECTS OF CATALYSTS
https://www.youtube.com/watch?v=i9TSLa3XNpQ
MICHAELIS-MENTEN KINETICS
In biological systems, enzymes act as catalysts and play a critical role in accelerating
reactions, anywhere from 103103 to 10171017 times faster than the reaction would
normally proceed. Enzymes are high-molecular weight proteins that act on a
substrate, or reactant molecule, to form one or more products. In
1913, Leonor Michaelis and Maude Menten proposed the following reaction
mechanism for enzymatic reactions:
 E+S⇌k−1k1ES→k2E+P

where EE is the enzyme, ESES is the enzyme-substrate complex, and PP is the

product. In the first step, the substrate binds to the active site of the enzyme. In the
second step, the substrate is converted into the product and released from the
substrate. For this mechanism, we can assume that the concentration of the
enzyme-substrate complex, is small and employ a steady-state approximation:

d[ES]dt=k1[E][S]−k−1[ES]ss−k2[ES]ss≈0

Furthermore, because the enzyme is unchanged throughout the reaction, we

express the total enzyme concentration as a sum of enzyme and enzyme-substrate
complex:

[E]0=[ES]+[E]

Plugging the above equations, we obtain

0=k1([E]0−[ES]ss)[S]−k−1[ES]ss+k2[ES]ss

Solving for [ES]ss[ES]ss

[ES]ss=k1[E]0[S]k1[S]+k−1+k2=[E]0[S][S]+k−1+k2k1

We can then write the reaction rate of the product as

d[P]dt=k2[ES]ss=k2[E]0[S][S]+k−1+k2k1=k2[E]0[S][S]+KM

where KMKM is the Michaelis constant. The equation given below is known as
the Michaelis-Menten equation. The result for Michaelis-Menten kinetics equivalent
to that for a unimolecular gas phase reaction catalyzed on a solid surface. In the limit
where there is a large amount of substrate present ([S]≫KM)([S]≫KM)

d[P]dt=rmax=k2[E]0

which is a 0th0th order reaction, since [E]0[E]0 is a constant. The

value k2[E]0k2[E]0 represents the maximum rate, rmaxrmax, at which the enzymatic
reaction can proceed. The rate constant, k2k2, is also known as the turnover
number, which is the number of substrate molecules converted to product in a given
time when all the active sites on the enzyme are occupied. Figure 29.9.4 displays the
dependence of the reaction rate on the substrate concentration, [S][S]. This plot is
known as the Michaelis-Menten plot. Examining the figure, we can see that the
reaction rate reaches a maximum value of k2[E]0k2[E]0 at large values of [S][S].
 Figure 29.9.4 : Rate dependence on substrate concentration for an enzymatic reaction.

Video to refer: https://www.youtube.com/watch?v=8PWF5OeB7Ec