Thermodynamics (1)

Thermodynamics is the branch of science
Which deals with Various forms

of energy are interrelated
Various forms of energy are

interrelated
Properties associated with bulk are called

macroscopic properties
THERMODYNAMICS
Flow of heat
Why Do We Need to Study Thermodynamics?
INTRODUCTION
 Thermodynamics evaluates the macroscopic properties (heat, work)
and their inter relationships.
 Investigation was the transformation of heat into mechanical work
 System : Part of universe which is under thermodynamic

consideration separated from the rest of the universe by
real or imaginary boundaries.
 Surrounding : Everything in the universe that is not the part of the

system
 Boundary : A real or imaginary layer separating the system from its

surroundings
HEAT- EXCHANGE OPEN
MATTER - EXCHANGE SYSTEM
HEAT – EXCHANGE CLOSED

MATTER NO EXCHANGE SYSTEM
EXCHANGE NEITHER ISOLATED

MATTER NOR ENERGY SYSTEM
IMPORTANT TERMS IN THERMODYNAMICS
• Heat (q) • Volume (V)
• Work (w) • Pressure (P)
• Internal energy (U) • Constant Pressure (Cp)
• Enthalpy (H) • Constant Volume (Cv)
• Entropy (S) • Gibbs free energy (G)
• Temperature (T)
Extensive Depends upon mass / size
Volume, Number of moles, Mass, Internal energy,
Properties
of
the
system
Intensive Independent of mass / size
Refractive index, Surface tension, density, temperature,

Boiling point, Freezing point
State of the System : Condition in which the system is present
State is defined by measuring the observable properties of the system
Eg : Pressure (P), Volume (V), Eg : Heat (q) ,Work (W), Time (Sec)
Temperature(T), Internal energy (U),
Enthalpy (H), free energy (G)
Adiabatic process q = 0
Isothermal process dT= 0
Thermodynamic
Thermodynamic processes
Isobaric process dP= 0
processes
Irreversible Process Isochoric process dV= 0
Cyclic process dE= 0, dH = 0, dP=0, dV=0 , dT=0
Process by which a system can change its state from one state of thermodynamic
equilibrium to another
Adiabatic process q = 0
GAS GAS Insulated wall
Pressure increase temperature increases because of internal energy of gas molecules increases.
No heat escape from inside / outside
GAS GAS
W.D on the system Compression W.D by the system Expansion

Isothermal process dT= 0
“ISO” – Same & Thermal - Temperature
GAS GAS
Pressure Temperature But here wall act as conducting material
P, V is change but Temperature is constant

Isobaric process dP= 0 Isochoric process dV= 0
“ISO” – Same & Bar – Pressure (Unit) “ISO” – Same & Bar – Pressure (Unit)
GAS
Pressure of the system remains constant Pressure increase But Volume is constant
Ex : Pressure cooker & Bomb Calorimeter
Cyclic process
dE= 0, dH = 0, dP=0, dV=0 , dT=0
After completing a series of changes, When system returns to original state

INTERNAL ENERGY (U)
In a system energy possessed by all its

constituents namely atoms, molecules
and ions
IMPORTANCE
Different Structure have different Internal
Total Energy = K.E + P.E + I.E Energy. (Diamond & Graphite)
Internal Energy (U) = Ut (Translational energy) + Uv (Vibrational energy) +

Ur (Rotational energy) + Ub (bond energy) +Ue (Electronic energy) +
Ui (energy due to molecular interactions)
CHARACTERISTICS OF THE INTERNAL ENERGY (U)
 Extensive properties (Additive)
Amount Internal energy

Double also doubled
 State function
 Change in internal energy (ΔU = Uf - Ui)
 ΔU = Uf < Ui -
ΔU = Uf > Ui +
 Cyclic process ΔU Cyclic = 0 (No Change)
HEAT (q)
Form of energy , Path function Bucket heat is decrease

Hand heat is increase
Heat transfer of hand from hot water.
Energy in transit across the boundary separating

a system from its surrounding
Heat Flows Energy of the system
Into the system Increase + q
Out of the system Decrease - q
Work (w)
It’s energy but transfer
Exchange
HEAT Work
of energy
Gas
Hot Water Non - Mechanical Mechanical
Work Done = Force × Displacement
 Path function (Not depend Initial to Final)
 Appears only at boundary of system & change of state
 Work unit = Joule (J)
Sign Convention
P ext
P ext
P int P ext < P int P ext > P int
Expansion P int
Compression
By the system On the system
Pressure – Work Volume
Work done during compression
V α1/P
W = F . dx P ext
P ext
P ext > P int = - F . Δx
P int
Compression = - Pext. A . Δx P int
On the system
= - Pext ΔV
Work is done on the system (+ w)
= - Pext. – Vi
= Pext ΔV (+ve)
Zeroth law of thermodynamics
If two systems are separately in thermal equilibrium with a third one, then they tend to be
in thermal equilibrium with themselves
If systems B and C separately are in thermal equilibrium with another

system A, then systems B and C will also be in thermal equilibrium
with each other
First law of thermodynamics
The first law of thermodynamics, known as the law of conservation of energy

The total energy of an isolated system remains constant though it may
change from one form to another
Energy can neither be created nor destroyed, but may be converted from one
form to another
The mathematical statement of the first law of thermodynamics
ΔU = U2 – U1.
ΔU = q + w (Change in I.E equal to Heat and Work)
Where q - the amount of heat supplied to the system; w - work done on the system
ΔU = q + w
Case 1 :
ΔU = q + w
For a cyclic process involving isothermal expansion of an ideal gas, ΔU = 0 So, q = -w
Case 2 :
ΔU = q + w
For an isochoric process (no change in volume) there is no work of expansion. i.e.
ΔV = 0
ΔU = q + w = q - PΔV
ΔU = qv
Problem
A gas contained in a cylinder fitted with a frictionless piston expands against a constant
external pressure of 1 atm from a volume of 5 litres to a volume of 10 litres. In doing so
it absorbs 400 J of thermal energy from its surroundings. Determine the change in
internal energy of system (1L atm = 101.33 J)
Enthalpy (H) H = U + PV
Isochoric process (no change in volume) there is no work of expansion.

i.e. ΔV = 0
ΔU = q + w
= q - PΔV ; ΔV = 0 ; ΔU = qv
Measure of heat is difficult at constant

Volume. We need to calculate
enthalpy equation
Relation between enthalpy `H' and internal energy `U'
H=U + PV
In the initial state

H1=U1 + PV1
As per first law of thermodynamics,
ΔU = q+w becomes ΔH = q + w + P ΔV
In the final state
w= -P ΔV
H2 = U2 + PV2
ΔH = qp – P ΔV + P ΔV
ΔH = q p
change in enthalpy is
(H2−H1) = (U2−U1) + P(V2−V1) qp− is the heat absorbed at constant pressure and is considered as
ΔH=ΔU + PΔV heat content.
Second law of thermodynamics
It is impossible to take heat from a hotter reservoir and convert a cyclic process heat to a cooler reservoir.
The second law of thermodynamics explains why even an ideal, frictionless engine cannot convert 100% of
its input heat into work.
Clausius statement
It is impossible to transfer heat from a cold reservoir to a hot reservoir without doing some work.
Third law of thermodynamics

States that the entropy of pure crystalline substance at absolute zero is zero.

Thermodynamics (1)

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Thermodynamics is the branch of science

Which deals with Various forms

Various forms of energy are

Properties associated with bulk are called

 System : Part of universe which is under thermodynamic

 Surrounding : Everything in the universe that is not the part of the

 Boundary : A real or imaginary layer separating the system from its

HEAT – EXCHANGE CLOSED

EXCHANGE NEITHER ISOLATED

• Heat (q) • Volume (V)

• Work (w) • Pressure (P)

• Internal energy (U) • Constant Pressure (Cp)

• Enthalpy (H) • Constant Volume (Cv)

• Entropy (S) • Gibbs free energy (G)

Volume, Number of moles, Mass, Internal energy,

Intensive Independent of mass / size

Refractive index, Surface tension, density, temperature,

Isothermal process dT= 0

Cyclic process dE= 0, dH = 0, dP=0, dV=0 , dT=0

GAS GAS Insulated wall

No heat escape from inside / outside

W.D on the system Compression W.D by the system Expansion

“ISO” – Same & Thermal - Temperature

Pressure Temperature But here wall act as conducting material

P, V is change but Temperature is constant

After completing a series of changes, When system returns to original state

In a system energy possessed by all its

Internal Energy (U) = Ut (Translational energy) + Uv (Vibrational energy) +

 Extensive properties (Additive)

Amount Internal energy

 Change in internal energy (ΔU = Uf - Ui)

Form of energy , Path function Bucket heat is decrease

Energy in transit across the boundary separating

Into the system Increase + q

Out of the system Decrease - q

 Path function (Not depend Initial to Final)

 Appears only at boundary of system & change of state

 Work unit = Joule (J)

If systems B and C separately are in thermal equilibrium with another

The first law of thermodynamics, known as the law of conservation of energy

Isochoric process (no change in volume) there is no work of expansion.

Measure of heat is difficult at constant

In the initial state

Third law of thermodynamics

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