PHYSICS

CHAPTER-THERMODYNAMICS

1. Some Important Terms Used in Thermodynamics

(i) System

 A system is the specific part of the universe chosen for study.

 It contains a fixed amount of matter enclosed within a boundary (real or
imaginary).

(ii) Surroundings

 Everything outside the system is called the surroundings.

 Surroundings may influence the system’s behavior.

(iii) Isolated System

 A system that does not exchange matter or energy with its surroundings.
 It is completely cut off from the environment.

Example: A perfectly insulated container.

(iv) Thermodynamic System

 A system whose state can be completely described using pressure (P),

volume (V), and temperature (T).

(v) Thermodynamic Variables

 Physical quantities used to describe the state of a thermodynamic system.

 The main variables are:

Pressure (P)

Volume (V)

Temperature (T)

(vi) Equation of State

 A mathematical relationship between thermodynamic variables (P, V, T).

Example: Ideal gas equation

PV=nRT

where n = number of moles of gas.

(vii) Thermal Equilibrium

 Two bodies are in thermal equilibrium if they have the same temperature.
 When two bodies at different temperatures are brought in contact:
 Heat flows from the hot body to the cold body.
 Flow continues until their temperatures become equal.
 At that point, they reach thermal equilibrium.

2. Concept of Temperature: Zeroth Law of Thermodynamics

Understanding the Setup

 Consider three systems: A, B, and C.

 A and B are separated by an insulated wall (cannot exchange heat).
 Both A and B separately come in contact with C through a conducting wall
(can exchange heat).

What Happens?

 A and C interact → They reach thermal equilibrium.

 B and C interact → They also reach thermal equilibrium.
 Later, if A and B are allowed to interact, their states do not change.

Conclusion

This leads to the Zeroth Law of Thermodynamics, which states:

Zeroth Law Statement

If two bodies A and B are each in thermal equilibrium with a third

body C, then A and B are in thermal equilibrium with each other.

Importance

 The Zeroth law gives the concept of temperature.

 It means all bodies in thermal equilibrium share a common characteristic →
temperature.
A. Temperature and Thermal Equilibrium (Conclusion)

1. Common Property in Thermal Equilibrium

All bodies in thermal equilibrium share a common physical quantity.

This common quantity is called temperature.

2. Definition of Temperature

Temperature is a property that tells us whether a body is in thermal equilibrium

with another body.

If two bodies have the same temperature, no heat flows between them.

3. Implication of Zeroth Law

If body A is in thermal equilibrium with body C and body B is also in thermal

equilibrium with body C,
then:

Therefore, A and B are in thermal equilibrium.

4. Importance

 Zeroth law helps define temperature as a measurable quantity.

Note

 R.H. Fowler introduced this law after the first two laws were already known.
 Therefore it was named Zeroth Law of Thermodynamics.

B. Equivalence of Work and Heat

1. Two Ways to Raise Temperature:

 We can increase the temperature of a body by:

 Heating (giving heat directly)

 Doing mechanical work on the body
2. Examples of Heating

 Warming hands in warm water

 Heating water over a flame
 Heating iron by placing in fire
 Stirring water (mechanical stirring produces heat)

3. Examples of Mechanical Work Producing Heat

 Pumping air → barrel becomes hot

 Rubbing a matchstick → ignites
 Hammering iron → becomes hot

4. Key Idea

 Both heat and mechanical work cause temperature rise.

 If temperature rise is the same, we cannot tell whether heat came from:
 heating
 or work
 Therefore, work is a form of heat energy.

C. Joule’s Experiment

1. Joule’s Findings

 Dr. Joule performed experiments to compare heat and work.

He discovered:

 Doing 4.18 × 10³ joules of work produces the same temperature rise as 1
kilocalorie of heat.

2. Conclusion

1 kilocalorie=4.18×103 joule

3. Smaller Unit Relation

1 calorie=4.18 joule

4. Mechanical Equivalent of Heat

 If Q calories of heat = W joules of work,

then:
W=4.18QW = 4.18 QW=4.18Q

5. Conversion Factor (J)

 The value 4.18 is called the mechanical equivalent of heat.

 It is represented by J.
 J is not a physical quantity, it is a conversion factor.

6. Equation Form

W=JQ

Where

J=4.18 J/cal

or 4.18×103 J/kcal

D. Heat, Work and Internal Energy

1. Heat

 Heat is energy transferred due to temperature difference.

 When a hotter body contacts a colder one:
 Heat flows from hot → cold
 Transfer continues until temperatures equal

2. Work

 Work is energy transfer that does not depend on temperature difference.

 Example: Compressing a gas, pulling a piston, etc.

Feature Heat Work

Temperature Applied force causing
Cause
difference displacement
Hot → Cold Can be in any direction,
Direction
automatically controlled
Requires temperature
YES NO
difference?
Thermal energy
Transfer mechanism Mechanical energy transfer
transfer
Example Boiling water gives Stirring water does work
 Feature Heat Work
heat

4. Example

 Hot body in contact with cold body → energy transferred = heat.

 Transfer continues until temperatures become equal.

1. Work Done by Stirring – Understanding the Concept

1. When a person stirs cold water in a vessel:

Energy is transferred from the person’s muscles → to the water.

Even if water does NOT feel warm, energy is still transferred.

This transferred energy is NOT called heat (because no temperature difference).

→ It is called work done on the water.

2. Temperature Difference Determines Heat Transfer

If temperature of the system ≠ temperature of surroundings → heat flows.

Flow continues until temperatures become identical.

When temperatures are equal → heat transfer stops.

Heat ALWAYS flows from higher temperature to lower.

2. Sign Convention for Heat

To avoid confusion, physics uses a standard sign rule:

(i) Heat given by the system to the surroundings

System loses heat → heat is taken as negative

 Q<0Q < 0Q<0

(ii) Heat taken by the system from surroundings

System absorbs heat → heat is taken as positive

 Q>0Q > 0Q>0

This sign convention is universal.

3. Work Done by a Gas – Detailed Explanation

A standard example is a cylinder with a movable piston.

Setup:

Gas is inside a cylinder.

A piston sits on top.

When weights are placed on the piston → gas is compressed.

When heat is supplied and weights removed → gas expands.

4. Work Done During Expansion of Gas

Consider:

Area of piston cross-section = A

Pressure of gas inside = P

5. Special Notes
6. Work from P–V Graph (Understanding Graphically)

The area under the P–V graph gives work done.

Case I: Constant Pressure (Isobaric Process)

If the P–V graph is a horizontal line:

Pressure = constant.

Volume changes from V1V_1V1 to V2V_2V2.

Work done = area of rectangle

W=P(V2−V1)W = P (V_2 - V_1)W=P(V2−V1)

This is visually represented as the shaded rectangular region in Fig. 3(a).

Case II: Pressure Varies (General Case)

When pressure changes continuously, the P–V graph becomes a curve, not a
straight line.

To calculate work:

Consider a tiny segment at any point M.

At that point, pressure = P, volume = V.

Take an extremely small change in volume → dV

Graphical Meaning:

The shaded curved area under the P–V graph = total work.

Even though pressure varies, area under curve still gives accurate work.

KEY IDEAS TO REMEMBER

1. Work is positive when gas expands

Because the gas is doing work on surroundings.

2. Work is negative when gas is compressed

Because surroundings are doing work on the gas.

3. Area under P–V graph always represents work

Rectangle for constant pressure.

Area under curve for variable pressure.

4. Work and heat differ by:

Heat needs temperature difference.

Work needs force × displacement.

1. Total Work Done During Expansion of Gas

When gas expands from volume V₁ to V₂, the work done is:
Explanation:

 The P–V curve represents how pressure changes with volume.

 The area enclosed between the P–V curve and the volume axis (from V₁ to V₂)
gives the total work done.
 Geometrically, work = area under the curve.

Key idea:

 If volume increases, work is positive (gas is doing work on surroundings).

 If volume decreases, work is negative (surroundings do work on gas).

2. Dependence of Work on the Path Taken

Important concept:

 Work done in a thermodynamic process depends not only on the initial

and final states but also on the path taken.

This means:

 Two different processes connecting the same states may do different

amounts of work.

Example (Based on Fig. 4)

 A system changes from initial state i to final state f using two different paths:
 Path i → a → f
 Path i → b → f

 Work along path iaf:

 Along a → f, volume increases while pressure remains constant.

 Area under rectangle iadc gives work done.

W=area of rectangle iadc

Work along path ibf:

Along i → b, volume doesn't change (V constant), hence no work is done.

W=0

Along b → f, volume increases at a different pressure.

Work along this part = area b f d c.

W′=area of rectangle bfdc

Comparing the two:

Area iadc is larger than area bfdc.

So,

 W>W′

Conclusion:

Even if initial and final states are same, work done depends on the
path of change.

3. Work Done in a Cyclic Process

What is a cyclic process?

 A process in which the system returns to its initial state after completing a
cycle.
 So, both pressure and volume return to original values.

Important feature:

 The P–V graph of a cyclic process forms a closed curve.

Example (Based on Fig. 5)

The system starts at state A.

Step 1 → Expansion (A to B)

 Gas expands from state A to B following curve ACB.

 Work done by the gas during expansion:
(This is the area under the curve A → C → B.)

Step 2 → Compression (B to A)

Now gas is compressed back to A following curve BDA.

Work done on the gas:

Since area BDAA'B' > area ACB B'A':

More work is done on the gas during compression than by the gas during
expansion.

Net Work in the Cycle:

Since W₍BA₎ > W₍AB₎ → net work is negative.

Meaning:

Net work is done on the system (the system consumes work).

4. Final Note (Very Important for Exams)

(i) If P–V curve is closed (cyclic):

Net work = area enclosed by the cycle.

(ii) Direction of tracing matters:

If cycle is traced clockwise →

Net work is done by the system (positive work).

If cycle is traced anti-clockwise →

Net work is done on the system (negative work).
In Fig. 5:

The process is traced anti-clockwise.

→ Therefore, net work is done on the gas.

4. Internal Energy

1. What is Internal Energy?

 Every bulk system (like gas, liquid, or solid) is made of a very large number of
molecules.

Each molecule has:

 Kinetic energy (due to motion)

 Potential energy (due to interactions)

2. Definition

 The internal energy (U) of a system is the total of all molecular KE + PE.
 It represents the microscopic energy stored inside the system.

3. Internal Energy Depends ONLY on State

 Internal energy depends on:

 Temperature (T)
 Pressure (P)
 Volume (V)
 These are called state variables.

4. Internal Energy Does NOT Depend On:

 The path taken to reach that state.

 How the state was achieved.
 Whether energy was added as heat, mechanical work, or both.

✔ Internal energy is a “state function.”

Meaning:

 It depends only on initial and final states, not on the process.

5. Example to Understand Internal Energy Change (ΔU)

Imagine a system (gas) changes from state A to state B.

Case 1: Path 1

 Let the heat taken = Q₁

 Work done by system = W₁
 Change in internal energy:

Case 2: Path 2

 Heat taken = Q₂
 Work done = W₂
 Change in internal energy:

Case 3: Path 3

Case 4: Path 4

Same reasoning.

Observation:

 In every case, the difference:

 Q−W=same constant value

 So all give:

✔ Therefore:

Change in internal energy depends only on the initial and final

states, not on the path.

Thus:
Conclusion from the Example

Internal energy (U) is a function of state.

If a system returns to its initial state:

ΔU=0

(Example: In a cyclic process, system returns to starting point → internal energy

does not change.)

Note (Very Important):

(i) Internal energy U is a property of state

 It does not change if system returns to same state.

 It is unique for every state.

(ii) If system goes through many processes and returns to original state → ΔU =
0

5. FIRST LAW OF THERMODYNAMICS

 This is one of the most important laws in physics.

Statement

 When a quantity of heat Q is supplied to a system:

 Part of it increases internal energy (ΔU)
 Rest is used to do work (W)

Mathematical Form

Q=ΔU+W

or,

ΔU=Q−W

Sign Convention:
Q positive → heat given to system

Q negative → heat taken from system

W positive → work done by system

W negative → work done on system

Internal Energy Change Between Two States A and B

Let internal energies be:

At A → U_A

At B → U_B

Then:

ΔU=UB−UA=Q-W

This is the first law of thermodynamics.

Differential Form (Infinitesimal Form)

For very small changes:

Heat added: dQ

Work done: dW

Internal energy change: dU

Then: dU=dQ−dW

This is extremely important for calculus-based thermodynamics.

Note on Units

All quantities must be in:

 Joules (J), or
 Calories (cal), or
 Kilocalories (kcal)

but the unit must be consistent throughout.

Sign Summary:

 If heat is given to system → Q is +

 If heat is released → Q is –
 If system does work → W is +
 If work is done on system → W is –

⭐ FINAL QUICK SUMMARY

Internal Energy

 Sum of molecular KE + PE
 Depends only on state (P, V, T)
 Independent of path

ΔU (Change in Internal Energy)

ΔU=Q−W

First Law of Thermodynamics

Heat supplied = Increase in internal energy + Work done by system

dU = dQ − dW

For very small processes.

Signs

✔ Q positive → heat added

✔ W positive → work done by system.

Applications of the First Law of Thermodynamics

The first law of thermodynamics is:

Q=ΔU+WQ = ΔU + WQ=ΔU+W

It explains how heat (Q), work (W), and internal energy (U) are related.

Let’s see how it applies to various special processes.

(i) Cyclic Process

1. What is a Cyclic Process?

 A system goes from an initial state → various states → back to the initial
state.
 Example: Complete cycle of a heat engine.

2. Key Point

 Since the system returns to its original state:

 ΔU=0

 Internal energy does not change because U depends only on state, not on the
path.

3. Applying First Law:

ΔU=Q−W

Putting ΔU = 0:

0=Q−W⇒Q=W

✔ Conclusion:

 In a cyclic process, the heat supplied to the system equals the net work
done by the system.
 This is why engines convert heat into work.

(ii) Isolated System

1. Definition

An isolated system:

 Cannot take heat from surroundings

 Cannot give heat
 Cannot do work on surroundings
 Cannot have work done on it

Thus:

Q=0,W=0

2. Applying First Law:

ΔU=Q−W=0−0=0
✔ Conclusion:

 Internal energy of an isolated system remains constant.

 No process can change its energy.

(iii) Isobaric Process (Constant Pressure)

1. Definition

 A process that occurs at constant pressure.

Examples:

 Heating water in a steam boiler

 Formation of steam
 Superheating of steam
 Freezing/melting at constant pressure

2. Vapourization Example

Mass m of a liquid at constant pressure and temperature is converted to vapour.

Heat taken:

Q=mL

where L = latent heat of vaporization.

3. Work Done During Expansion

When liquid turns to vapour, its volume increases from V₁ → Vᵥ.

Interpretation
 The heat supplied (mL) is used in two parts:
 Increasing internal energy of vapour → internal latent heat
 Doing work against external pressure → external latent heat

Freezing Example

Water freezes and becomes ice.

Heat Given Out

Q=−mLfQ

(L = latent heat of freezing)

Negative sign because heat is released by the system.

Volume Increases While Freezing

Water expands during freezing:

W=P ΔV

Work is done by the water.

Change in Internal Energy

ΔU=Q−W=−mL−PΔV

This is negative.

✔ Conclusion

When water freezes, its internal energy decreases.

The decrease is larger than the heat released.

(iv) Isochoric Process (Constant Volume)

1. Definition

A process occurring at constant volume.

ΔV=0

2. Since volume is constant:

 W=P×ΔV=0

No work is done.

3. Applying First Law

Q=ΔU

✔ Conclusion

 In an isochoric process, all the heat supplied goes into changing internal
energy.

(v) Isothermal Process (Constant Temperature)

1. Definition

An isothermal process is a thermodynamic process in which:

Temperature remains constant throughout the process.

2. Internal Energy in an Ideal Gas

For an ideal gas:

Internal energy depends only on temperature, not on volume or pressure.

So, if temperature is constant → internal energy is constant.

Thus:

ΔU=0

3. Applying the First Law

First law:

Q=ΔU+W

Since ΔU = 0:

Q=W

✔ Conclusion
In an isothermal process for an ideal gas, the heat absorbed (Q) is exactly
equal to the work done (W) by the gas.

Meaning:

 The gas uses all the heat it receives to do work.

 It does not increase its internal energy.

Note:

This is strictly valid only for ideal gases, not for real gases.

(vi) Adiabatic Process (No Heat Exchange)

1. Definition

An adiabatic process is one in which:

No heat enters or leaves the system.

Thus:

Q=0

This may happen due to:

 Perfect insulation
 Very fast compression/expansion (process too quick for heat transfer)

2. Applying First Law

Q=ΔU+W

Putting Q = 0:

0=ΔU+W

So:

ΔU=−W

Interpreting the Formula

There are two cases:

Case 1: Work is done on the system

W is negative
(Because work done on the system is taken as negative in sign convention)

Put W = –|W|:

ΔU=−(−∣W∣)=∣W∣

✔ Conclusion:

Internal energy increases when work is done on the system.

Thus, temperature rises.

Example:

Shaking a thermos of hot tea:

No heat leaves or enters (good insulation).

But shaking does mechanical work.

Internal energy increases → tea becomes hotter.

Case 2: Work is done by the system

W is positive
(Because gas expands and pushes surroundings)

ΔU=−W

✔ Conclusion:

Internal energy decreases when the system does work.

Thus, temperature falls.

Example:

 A tyre bursts:
 Air inside expands suddenly and rapidly.
 No heat exchange (adiabatic).
 Air does work pushing atmosphere.
 Air becomes cooler.
⭐ Understanding Adiabatic Processes with Everyday Examples

1. Shaking a thermos of tea

 No heat exchange.
 Mechanical work is done on liquid.
 Temperature increases → internal energy increases.

2. Bursting a tyre

 Sudden expansion.
 No time for heat exchange.
 Gas does work on air outside.
 Internal energy decreases → air cools.
 These examples show how work affects internal energy in adiabatic
processes.

Property Isothermal Adiabatic

Temperature Constant Changes
Heat exchange Possible Zero (Q = 0)
ΔU 0 –W
Formula Q=W ΔU = –W
Internal energy Constant Changes