Chemical thermodynamics

Chemical thermodynamics focuses specifically on energy changes that occur in
chemical reactions. It provides a quantitative description of the thermodynamic

properties of chemical systems and their changes during chemical reactions.
The key concepts in chemical thermodynamics include energy, enthalpy, entropy, free
energy, and equilibrium.
A battery stores electrical energy that can be used to power a device.

The movement of a car is a result of the conversion of chemical energy in gasoline
into mechanical energy.
A cup of hot coffee contains thermal energy that can be used to do work.
Enthalpy is a measure of the heat content of a system at constant pressure. It is

represented by the symbol H and is usually expressed in units of joules or
calories.
In an exothermic reaction, heat is released by the system into the surroundings,

and therefore, the enthalpy change is negative.
endothermic reactions have a positive change in enthalpy, as they absorb heat from
the surroundings.
Entropy is a measure of the disorder or randomness of a system. It is represented

by the symbol S and is usually expressed in units of joules per Kelvin. Some
examples of entropy are:
When a gas expands into a larger volume, its entropy increases because there are
more possible positions and velocities for its molecules.
When ice melts into water, its entropy increases because the molecules have more
freedom of movement.
Spontaneous reactions are chemical reactions that occur without any external
influence, such as the addition of energy or a catalyst. These reactions occur
naturally and proceed in a particular direction without any intervention.
the second law of thermodynamics tells us that things naturally tend to become less
organized and less useful over time, and that energy can never be completely
recycled without some waste.
Gibbs free energy (often denoted as G) is a thermodynamic quantity that measures

the amount of energy available to do work in a system at constant temperature and
pressure. It is named after the American scientist Josiah Willard Gibbs, who
developed the concept.
Gibbs free energy is defined as:
G = H - TS
where H is the enthalpy (total heat content) of the system, T is the temperature in
Kelvin, and S is the entropy (degree of disorder) of the system.
It tells us how much useful energy a system has that can be used to perform work.
If the Gibbs free energy decreases during a process, it means the process can occur
spontaneously without the input of external energy. On the other hand, if the Gibbs
free energy increases during a process, it means that the process is non-
spontaneous and requires external energy input. Gibbs free energy is a key concept
used to predict the behavior of chemical reactions and materials science, and to
design efficient processes for energy conversion.
simple practice problem:
What is the standard free energy change for the reaction:
2H2(g) + O2(g) → 2H2O(l)
Given:
ΔH° = -484 kJ/mol
ΔS° = -228 J/(mol K)
Temperature (T) = 298 K
Solution:
We can use the equation: ΔG° = ΔH° - TΔS° to calculate the standard free energy
change.
ΔG° = (-484 kJ/mol) - (298 K)(-228 J/(mol K)) / (1000 J/kJ)

ΔG° = -482.3 kJ/mol
Since the calculated value is negative, the reaction is spontaneous under standard
conditions.
a negative ΔG° indicates that a reaction is spontaneous and will proceed in the
forward direction, while a positive ΔG° indicates that the reaction is non-
spontaneous and will proceed in the reverse direction.
A superscript circle ° (degree symbol) or a Plimsoll (⦵) character is used to

designate a thermodynamic quantity in the standard state
The equilibrium constant for the reaction below is 0.25 at 298 K. Calculate the
equilibrium constant at 350 K if the enthalpy change for the reaction is -100
kJ/mol and the entropy change is -200 J/(mol·K).
A + B ⇌ C + D
Solution:
We can use the Van't Hoff equation to calculate the equilibrium constant at a
different temperature:
ln(K2/K1) = ΔH°/R [1/T1 - 1/T2]
where K1 is the equilibrium constant at the initial temperature T1, K2 is the

equilibrium constant at the new temperature T2, ΔH° is the enthalpy change of the
reaction, R is the gas constant (8.314 J/(mol·K)), and ln is the natural logarithm.
Substituting the given values, we get:
ln(K2/0.25) = (-100000 J/mol) / (8.314 J/(mol·K)) [1/298 K - 1/350 K]
Solving for ln(K2/0.25), we get:
ln(K2/0.25) = -23.776
Taking the exponential of both sides, we get:
K2/0.25 = e^(-23.776)
Solving for K2, we get:
K2 = 0.000022
Therefore, the equilibrium constant at 350 K is 0.000022.
Increase in entropy means an increase of chaos or disorganization in a system and

a decrease of enthalpy means heat is released into the surroundings (exothermic
reactions) ex. Fire
Decrease in entropy means more order and structure in a system and an increase in
enthalpy means heat is absorbed from the surroundings (endothermic) e. Ice cubes
melting
there are some exceptions to this rules and we will use ice and water as an
example.
let us look at the movement of ice to water.
Ice has a lot order while water is more flexible.

If we melt ice, we will have a positive enthalpy and a positive entropy. heat is
absorbed from the surroundings to melt the ice and when its turning to water, it
becomes disordered. (Spontaneous at high temp)
Water to Ice is the vice versa. Freezing is decreasing the entropy making it
ordered, and when water becomes a solid, it releases heat, warming up its
surroundings, decreasing its enthalpy. (Spontaneous at low temp)

Chemical thermodynamics

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Chemical thermodynamics focuses specifically on energy changes that occur in

chemical reactions. It provides a quantitative description of the thermodynamic

A battery stores electrical energy that can be used to power a device.

Enthalpy is a measure of the heat content of a system at constant pressure. It is

In an exothermic reaction, heat is released by the system into the surroundings,

Entropy is a measure of the disorder or randomness of a system. It is represented

Gibbs free energy (often denoted as G) is a thermodynamic quantity that measures

Gibbs free energy is defined as:

What is the standard free energy change for the reaction:

2H2(g) + O2(g) → 2H2O(l)

ΔG° = (-484 kJ/mol) - (298 K)(-228 J/(mol K)) / (1000 J/kJ)

A superscript circle ° (degree symbol) or a Plimsoll (⦵) character is used to

ln(K2/K1) = ΔH°/R [1/T1 - 1/T2]

where K1 is the equilibrium constant at the initial temperature T1, K2 is the

Substituting the given values, we get:

ln(K2/0.25) = (-100000 J/mol) / (8.314 J/(mol·K)) [1/298 K - 1/350 K]

Solving for ln(K2/0.25), we get:

Taking the exponential of both sides, we get:

Therefore, the equilibrium constant at 350 K is 0.000022.

Increase in entropy means an increase of chaos or disorganization in a system and

let us look at the movement of ice to water.

Ice has a lot order while water is more flexible.

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