GRADE 11 – THERMODYNAMICS

The System and the Surroundings:

A system in thermodynamics refers to that part of universe in which observations are made.
The surroundings include everything in the universe other than the system.
System and the surroundings together constitute the universe.
The wall that separates the system from the surroundings is called boundary.
Types of the System
Open System: In an open system, there is exchange of energy and matter between system and
surroundings.
Closed System: In a closed system, there is no exchange of matter, but exchange of energy is
possible between system and the surroundings.
Isolated System: In an isolated system, there is no exchange of energy or matter between the
system and the surroundings.
The state of a thermodynamic system is described by its measurable properties. We can
describe the state of a gas by quoting its pressure (p), volume (V), temperature (T), amount
(n) etc.
Variables like p, V, T are called state variables or state functions because their values
depend only on the state of the system and not on how it is reached.

The Internal Energy (U) as a State Function:

The total energy of the system is known as the internal energy of the system. It may be
chemical, electrical, mechanical or any other type of energy, the sum of all these is the
energy of the system.
The internal energy, U, which may change, when
• heat passes into or out of the system
• work is done on or by the system
• matter enters or leaves the system
Adiabatic process is a process in which there is no transfer of heat between the system and
surroundings.
The q is positive, when heat is transferred from the surroundings to the system and the
internal energy of the system increases
The q is negative when heat is transferred from system to the surroundings resulting in
decrease of the internal energy of the system.

Let us consider the general case in which a change of state is brought about both by doing
work and by transfer of heat. The change in internal energy for this case is
∆U = q + w
This is the mathematical statement of the first law of thermodynamics, which states that
the energy of an isolated system is constant.
It is commonly stated as the law of conservation of energy i.e., energy can neither be created
nor be destroyed.
Enthalpy (H)
The heat absorbed at constant volume is equal to change in the internal energy i.e., ∆U = qV.
But most of chemical reactions are carried out not at constant volume, but in flasks or test
tubes under constant atmospheric pressure.
∆ U = qp – p ∆ V at constant pressure, where qp is heat absorbed by the system and –p∆V
represent expansion work done by the system.
∆H = qp, heat absorbed by the system at constant pressure.
∆H = ∆U + p∆V
∆H is negative for exothermic reactions which evolve heat during the reaction.
∆H is positive for endothermic reactions which absorb heat from the surroundings.
At constant volume (∆V = 0), ∆U = qV,
Therefore ∆H = ∆U = qV
Let us consider a reaction involving gases. If VA is the total volume of the gaseous reactants,
VB is the total volume of the gaseous products, nA is the number of moles of gaseous
reactants and nB is the number of moles of gaseous products, all at constant pressure and
temperature, then using the ideal gas law, we write,
pVA = nART and
pVB = nBRT
Thus, pVB – pVA = nBRT – nART
= (nB–nA) RT
p ∆V = ∆ngRT (6.9) Here, ∆ng refers to the number of moles of gaseous
products minus the number of moles of gaseous reactants.
Therefore, ∆H = ∆U + ∆ngRT
Extensive and Intensive Properties:
An extensive property is a property whose value depends on the quantity or size of matter
present in the system.
Eg: mass, volume, internal energy, enthalpy, heat capacity, etc.
Intensive property is a property which do not depend on the quantity or size of matter present
in the system.
Eg: temperature, density, pressure etc.
Heat Capacity
When heat is transferred to a system, the heat appears as a rise in temperature of the system.
The increase of temperature is proportional to the heat transferred.
q = coeff x ΔT
i.e. q = C ∆T, the coefficient, C is called the heat capacity.
Specific heat, also called specific heat capacity (c) is the quantity of heat required to raise
the temperature of one-unit mass of a substance by one-degree celsius (or one kelvin).
q = c x m x T = C ΔT
The Relationship between Cp and CV for an Ideal Gas:
At constant volume, the heat capacity, C is denoted by CV and at constant pressure, this is
denoted by Cp.
at constant volume as qV = CvΔT = ΔU
at constant pressure as qp = CpΔT = ΔH
For a mole of an ideal gas, ∆H = ΔU + pΔV
=ΔU + RΔT
 ∴ ∆H = ∆U + R∆T
On putting the values of ∆H and ∆U, we have
CpΔT = CvΔT + RΔT
Cp = CV + R
Cp – CV = R
ENTHALPY CHANGE, ∆rH OF A REACTION – REACTION ENTHALPY:
The enthalpy change accompanying a reaction is called the reaction enthalpy.
a) Standard Enthalpy of Reactions ∆rHƟ
The enthalpy changes for a reaction when all the participating substances are in their
standard states.
[The standard state of a substance at a specified temperature is its pure form at 1 bar.]
b) Enthalpy Changes during Phase Transformations
The enthalpy change that accompanies melting of one mole of a solid substance in standard
state is called standard enthalpy of fusion, ∆fusHƟ.
The enthalpy change that accompanies the vaporization of one mole of a liquid at constant
temperature and under standard pressure (1bar) is called its standard enthalpy of
vaporization, ∆vapHƟ.
The enthalpy change that accompanies when one mole of a solid substance sublimes at a
constant temperature and under standard pressure (1bar) is called its standard enthalpy of
sublimation, ∆subHƟ.
c) Standard Enthalpy of Formation, ∆fHƟ
The standard enthalpy changes for the formation of one mole of a compound from its
elements in their most stable states.
d) Hess’s Law of Constant Heat Summation
If a reaction takes place in several steps, then its standard reaction enthalpy is the sum of the
standard enthalpies of the intermediate reactions into which the overall reaction may be
divided at the same temperature.
ENTHALPIES FOR DIFFERENT TYPES OF REACTIONS
a) Standard Enthalpy of Combustion, ∆cHƟ
Enthalpy change per mole of a substance, when it undergoes combustion and all the reactants
and products being in their standard states at the specified temperature is called standard
enthalpy of combustion.
b) Enthalpy of Atomization, ∆aHƟ
Enthalpy change on breaking one mole of bonds completely to obtain atoms in the gas phase
is called standard enthalpy of atomization.
d) Lattice Enthalpy, ∆latticeHƟ
The lattice enthalpy of an ionic compound is the enthalpy change which occurs when one
mole of an ionic compound dissociates into its ions in gaseous state.

e) Enthalpy of Solution, ∆solHƟ

Enthalpy of solution is the enthalpy change when one mole of solute dissolves in a specified
amount of solvent.
f) Enthalpy of Dilution
Enthalpy of solution is the enthalpy change associated with the addition of a specified
amount of solute to the specified amount of solvent at a constant temperature and pressure.
SPONTANEITY
A reaction having the potential to proceed without the assistance of external agency is called
spontaneous reaction.
a) Decrease in Enthalpy
Decrease in energy is considered as a driving force for a chemical reaction to be
spontaneous.
b) Entropy (S)
Entropy as a measure of the degree of randomness or disorder in the system. The greater the
disorder in an isolated system, the higher is the entropy.
When a system is in equilibrium, the entropy is maximum, and the change in entropy, ∆S =
0.
c) Gibbs Energy and Spontaneity
Neither decrease in enthalpy nor increase in entropy alone can determine the direction of
spontaneous change for these systems.
we define a new thermodynamic function the Gibbs energy or Gibbs function, Gas
G = H – TS
Gibbs function, G is an extensive property and a state function.
The change in Gibbs energy for the system,
∆G = ∆H - T∆S
∆G gives a criterion for spontaneity at constant pressure and temperature.
i) If ∆G is negative (< 0), the process is spontaneous.
ii) If ∆G is positive (> 0), the process is non-spontaneous.
GIBBS ENERGY CHANGE AND EQUILIBRIUM
The knowledge of the sign and magnitude of the free energy change of a chemical reaction
allows:
i) Prediction of the spontaneity of the chemical reaction.
ii) Prediction of the useful work that could be extracted from it.
So, the criterion for equilibrium A + B C + D is
∆rG = 0
Gibbs energy for a reaction in which all reactants and products are in standard state, ∆ rGƟ is
related to the equilibrium constant of the reaction.
0 = ∆rGƟ + RT ln K
∆rGƟ = – RT ln K
∆rGƟ = – 2.303 RT log K
We also know that

∆G = ∆H - T∆S = -RTlnK