THERMODYNAMICS

GRADE: 11
Mr Rajat Saini
 INTRODUCTION
The term thermo means heat and dynamics means motion.
Thermodynamics is a branch of science which deals with different forms of energy and their
inter conversion.

THERMODYNAMIC TERMS
 System: The part of universe selected for thermodynamic study.
 Surroundings: The remaining part of universe around the system which is not under the study.
 Boundary: The wall that separates system from surroundings is called boundary. Boundary
may be (i) Flexible or Rigid (ii) Real or imaginary (iii) Adiabatic (non conducting) or
diathermic (conducting)
Ex: Air is flexible balloon (Flexible Boundary)
Air is a room (Fixed/Rigid boundary)
 Universe: System and Surroundings together constitute the universe.
Universe = System + Surroundings
 TYPES OF SYSTEMS
Depending upon the exchange of mass and energy between system and surroundings, there are
three types of systems.
Open System: In an open system, there is exchange of energy and matter between system and
surroundings. The presence of reactants in an open beaker is an example of an open system.
Closed System: In a closed system, there is no exchange of matter, but exchange of energy is
possible between system and the surroundings. The presence of reactants in a closed vessel
made of conducting material like copper or steel is an example of a closed system.
Isolated System: In an isolated system, there is no exchange of energy or matter between the
system and the surroundings. The presence of reactants in a thermos flask or any other closed
insulated vessel is an example of an isolated system.
Macroscopic System: A system which consist of large number of atoms, ions or molecules is called
macroscopic system.
Macroscopic Properties: The properties which depend upon bulk behavior of matter are called
macroscopic properties. Thermodynamics deals with macroscopic properties only.
Two Types of Macroscopic Properties:
1) Extensive Properties 2) Intensive Properties
Extensive Properties: The properties which depends upon the amount of substance or matter present in
a system are called extensive properties.
Ex: Mass, Volume, Heat Capacity, Internal Energy, Enthalpy, Entropy, Gibb’s Energy.
Extensive Properties are additive.
Intensive Properties: The properties which depend upon the nature of substance and are independent of
the amount of the substance present in the system are called intensive properties.
Ex: Temperature, Density, Specific Heat, Refractive index, pH, Freezing Point, Boiling Point, Molarity,
Normality, Standard Reduction potential.
Intensive Properties are non additive.
Note: An extensive property may become intensive property by specifying unit amount of the substance
concerned. Thus mass and Volume are extensive properties but density (Mass/Volume) and specific volume
(Volume/Mass) are intensive properties. Heat capacity is extensive but specific heat is intensive.
 State of System
We need to describe the system by specifying it before and after the change.
The system must be described in order to make any useful calculations by specifying quantitatively each
of the properties such as its pressure (p), volume (V), and temperature (T) as well as the composition of
the system.
In order to completely define the state of a system it is not necessary to define all the properties of the
system; as only a certain number of properties can be varied independently.
State Variables: Measurable properties required to describe the state of a system are called state
variables. 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 state variables.
State Variable may be State Function or Path Functions
State Function: It is a property of the system whose value depends only upon the state of the system and
does not depend upon the path by which this state has been achieved.
Ex: Pressure(P), Temperature(T), Internal Energy(U), Entropy(S), Gibb’s Energy(G), Volume(V),
Enthalpy(H) etc.
Example: Volume of water in a pond, Because change in volume of its water is independent of the routes
by which water is filled in the pond, either by rain or by tube well or by both.
Example: Temperature is a state function because the change in temperature is independent of the route
taken.
Path Functions: It is a property of system whose value depends upon manner in which the
change has been brought is called a path function.
Ex: Work (w), Heat (q)
State functions are denoted by Capital Letters, While Path functions are denoted by small letters

Distance is Path function whereas displacement is a state function

 Thermodynamic process
A thermodynamic process is said to have occurred when a system undergoes a change in its state. The different types
of processes are:

 An isothermal process occurs when the system has conducting walls or it is an open system. The container with
conducting walls is called diathermic.
 Isothermal process cannot take place in isolated system.
 An adiabatic process occurs when it is a closed system and has non-conducting (insulated) walls, called adiabatic
walls.
 Change in the value of any state function in a cyclic process is zero. But path functions are not zero.
 Internal Energy or Intrinsic Energy
Sum of different forms of energy like kinetic energy, potential energy, nuclear energy, chemical
energy etc. associated with the molecules is called the internal energy or intrinsic energy of
system. It was denoted by E but according to latest IUPAC system, it is denoted by the letter, U.

Characteristics
 It is a State function
 It is an extensive property
 Absolute value of internal energy of a system cannot be determined because it is not possible to determine the
exact values of constituent energies such as translational energy, nuclear energy, vibrational energy etc. However,
we only deal with change in energy during a chemical reaction. It may be considered as the difference between the
internal energies of products and reactants.
∆U = 𝑈𝑈𝑝𝑝 - 𝑈𝑈𝑟𝑟
 Internal energy of the system may change, When
(i) heat passes into or out of the system,
(ii) work is done on or by the system,
(iii) matter enters or leaves the system.
 Internal energy of an ideal gas is a function of temperature. So, during an isothermal processes involving ideal gas,
as temperature remains constant, So internal energy also remains constant.
i.e. U = Constant ∆U = 0
Work:
 It is a mode of energy transfer to or from a system with reference to the surroundings.
 If an object is displaced through a distance dx against a force of F, then the amount of work
done is defined as W = F × dx
Characteristics:
 Work (w) is a path-dependent function.
 Work done on a system increases the energy of the system and work done by the system decreases the energy of
the system.
Work done on the system, w = + ve
Work done by the system, w = -ve
 Work associated with change in volume of a system against external pressure is called mechanical work.
 The mechanical work done during a process is given by the area under the P vs V graph for the process.
 Units of work : Units of work are same as those of energy, e.g., ergs, joules

1 J = 1 Nm = 1 kgm2s-2
 Change in internal energy by doing work
If work is done on the system, state of the system and internal energy can be changed in two
different methods:

Method 1 Method 1
1 kJ mechanical work done by rotating a set of small 1 kJ electrical work done by immersion rod as shown.
paddles and thereby churning water as shown.
Initial State: T = TA & U = UA
Initial State: T = TA & U = UA

Final State: T = TB & U = UB

TB > TA
Final State: T = TB & U = UB
Change in internal energy = ∆U = 𝑈𝑈𝐵𝐵 - 𝑈𝑈𝐴𝐴
TB > TA
Change in internal energy = ∆U = 𝑈𝑈𝐵𝐵 - 𝑈𝑈𝐴𝐴
 Conclusion
According to Joule, no matter how the work is done (irrespective of path), it produce the same
change of state which is measured by the change in temperature of the system.
So it seems appropriate to define a quantity, the internal energy U whose value is characteristic
of the state of a system, whereby the adiabatic work (Wad) required to bring about a change of
state is equal to the difference between the value of U in one state and that in another state.
∆U = 𝑈𝑈2 - 𝑈𝑈1 = Wad
Therefore U is a state function, whereas work done itself is a path function.
 Reversible Processes
A process which is carried out infinitesimally slowly so that all changes occurring in a direct
process can be exactly reversed and the system remains almost in equilibrium with surroundings
at every stage of the process is called a reversible process.
During a reversible process, the driving force is slightly greater than the opposing force so that
at all stages, the process can be reversed by an infinitesimally small change i.e. by increasing the
driving force slightly.
Reversible process, is in equilibrium at all stages.
Work obtained is maximum in reversible expansion.
It is difficult to realise in practice.
 Irreversible Processes
A process is said to be irreversible if it is not carried out infinitesimally slowly (instead it is
carried out rapidly) so that any change in the external condition disturbs the equilibrium.
In such process, the driving force is much larger than opposing force.
It is spontaneous process and takes finite time for completion.
Equilibrium exists in the initial and final stages only.
Work obtained is not maximum in irreversible expansion.
It can be performed in practice.
What are the two types of work done a system can undergo?

A system can do two types of work

1) Electrical Work (Volume Constant)
2) Mechanical Work (Volume Changes)
In thermodynamics, we consider only mechanical work, that is
Pressure – Volume work
Consider a cylinder containing one mole of a gas fitted with a frictionless piston.
Let the cross – sectional area of piston = A
During expansion, Piston moves a distance = dx
Ques: A gas expands by 0.5 litre against a constant pressure of one atmosphere. Calculate
the work done in joule and calorie.

Ques: Calculate the maximum work done in expanding 16 g of oxygen at 300 K and occupying
a volume of 5 dm3 isothermally until the volume becomes 25 dm3.
 FIRST LAW OF THERMODYNAMICS
 FLOT states that energy can neither be created nor be destroyed. It can only be transformed from one form to the
other.
Mathematically; ∆U = q + w
 In an isolated system, there is no exchange of matter or energy with the surrounding. So,
q=0 w=0
∆U = 0
That is energy of an isolated system is constant.
The change of state may be isobaric, isochoric, isothermal or adiabatic.
 If change of state is isochoric, i.e. V1 = V2
∆V = 0
w=0
∆U = 𝑞𝑞𝑣𝑣 + 0
i.e. during isochoric process heat supplied to the system (𝑞𝑞𝑣𝑣 ) is equal to the change in internal energy (∆U)
If change of state is isobaric, i.e.
∆U = 𝑞𝑞𝑝𝑝 + w
Heat evolved or absorbed in a process at constant pressure (𝑞𝑞𝑝𝑝 ) is known as enthalpy change, ∆𝐻𝐻
∆U =∆𝐻𝐻 + w
∆𝐻𝐻 = ∆U - w
∆𝐻𝐻 = ∆U – ( – P∆V)
∆𝐻𝐻 = ∆U + P∆V
Where ∆𝐻𝐻 = heat change at constant pressure
∆U = Heat change at constant volume
𝑞𝑞𝑝𝑝 = 𝑞𝑞𝑣𝑣 + P∆V
𝑞𝑞𝑝𝑝 − 𝑞𝑞𝑣𝑣 = P∆V
Difference between energy at constant pressure and constant volume is equal to work done.
In a chemical reaction, where all the components are liquids, solids or in solutions (System with
no gas). Volume changes are very very small and P∆V can be neglected.
 Heat
It is the quantity of energy which is transferred between the system and its surroundings as a result of
temperature difference.
We can change the internal energy of a system by transfer of heat between the surroundings and the
system.
Sign convention:
When is gained by the system, q is +ve (i.e. if the process is endothermic)
When is lost by the system, q is –ve (i.e if the process is exothermic)
What is meant by heat capacity, specific heat capacity and molar heat capacity?
In order to measure the heat changes the heat capacity is used.
Heat transfer results in change of temperature. The change in temperature is proportional to the heat
transferred, i.e
q ∝ ∆𝑇𝑇
q = C∆𝑇𝑇
𝑞𝑞
C=
∆𝑇𝑇
The heat capacity is the heat needed to raise the temperature of a substance by 1K or 10C.
Unit of heat capacity: JK-1
Specific Heat Capacity is the heat needed to raise the temperature of a unit mass of substance by 1K or 10C.
 Relation between Cp and Cv
We know that Heat capacity is given
q ∝ ∆𝑇𝑇
q = C∆𝑇𝑇
At Constant pressure: 𝑞𝑞𝑝𝑝 = 𝐶𝐶𝑝𝑝 ∆𝑇𝑇
The heat transferred at constant pressure (𝑞𝑞𝑝𝑝 ) by a chemical process is known as enthalpy change, ∆𝐻𝐻
𝑞𝑞𝑝𝑝 = ∆𝐻𝐻 = 𝐶𝐶𝑝𝑝 ∆𝑇𝑇
At constant volume: 𝑞𝑞𝑣𝑣 = 𝐶𝐶𝑣𝑣 ∆𝑇𝑇
Now;
Enthalpy change during Physical and Chemical Processes
The enthalpy change, ∆𝐻𝐻 for a process is the heat transferred between the reacting system and
the surroundings at constant pressure (𝑞𝑞𝑝𝑝 ).
The enthalpy change for various process is denoted by ∆𝑟𝑟 H.
The value of ∆𝑟𝑟 H depends upon temperature and pressure at which the process occurs as well as
the physical state of the components.
Thus, a set of standard conditions is described to allow comparison between the values. The
standard conditions are:
1) A Pressure of 1 Bar.
2) The reactants and Products in their standard state. That is pure at 1 bar pressure or 1M
concentration for a solution.
The value of ∆𝑟𝑟 H0 are written at a specific temperature, usually 298K and always have positive
and negative sign to show whether the process is exothermic or endothermic.
For Example: Standard state of liquid ethanol at 298K is pure liquid ethanol at 1 bar.
Standard state of pure iron at 500K is pure iron at 1 bar.
 Factors affecting the enthalpy of a reaction ∆𝑟𝑟 H
Physical state of reactant and products: Since latent heat is involved in the change in the
physical states of the reactants and products, therefore enthalpy (or heat) of a reaction change
with the change in physical state.
For example:

 Quantities of reactants: The change in enthalpy or amount of heat energy evolved or absorbed
depends upon the quantities or amounts of the reactants taking part in the reaction.
For example:
Allotropic modifications of reactants: The enthalpy of reactions are different for the different
allotropic forms of a particular substance.
For example:
 MEASUREMENT OF ∆U AND ∆H: CALORIMETRY
The energy changes associated with chemical or physical process can be measured by calorimetry.
Calorimetry is carried out in a vessel called calorimeter, which is immersed in a known volume of a
liquid. The two common types of calorimeters are:
1) Bomb Calorimeter
2) Coffee cup calorimeter
Measurements are made under two conditions:
1) At constant volume (qv = ∆U)
2) At constant pressure (q p = ∆H)
1) Bomb Calorimeter (∆U measurement)
 For a chemical reaction, heat absorbed at constant volume is
measured in a Bomb calorimeter.
 A combustible substance is burnt in-pure dioxygen supplied in the
steel bomb.
 Heat evolved during the reaction is transferred to the water around the
bomb and its temperature is monitored. Since the bomb calorimeter is
sealed its volume does not change i.e., the energy changes associated
with reactions are measured at constant volume.
Under these conditions, no work is done as the reaction is carried out at constant volume in the
calorimeter.
Even for reactions involving gases, there is no work done as ∆V = O. Temperature change of the
calorimeter produced by the completed reaction is then converted to qv , by using the known heat
capacity of the calorimeter.

Where, M is the molar mass of the substance, m is the mass of the substance taken and z is heat
capacity of the calorimeter.
2) Coffee cup calorimeter (∆H measurement)
 Measurement of heat change at constant pressure (generally under
atmospheric pressure) can be done in a calorimeter shown.
 We know that ∆H = qp (at constant p)
 qp at constant pressure is also called the heat of reaction or enthalpy of
reaction, ∆𝑟𝑟 H.
 In an exothermic reaction, heat is evolved, and system loses heat to the
surroundings. Therefore, qp will be negative and ∆𝑟𝑟 H will also be negative.
 Similarly in an endothermic reaction, heat is absorbed, qp is positive and
∆𝑟𝑟 H will be positive.
Enthalpy change during Physical Processes (Phase Transformation)
Enthalpy changes during a chemical Processes
BOND ENTHALPY
SECOND LAW OF THERMODYNAMICS