Lecture No.3

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Thermal Equilibrium

Two bodies are said to be at thermal equilibrium if they are at the same
temperature. This means there is no net exchange of thermal energy between the
two bodies. The top pair of objects are in contact, but since they are at different
temps, they are not in thermal equilibrium, and energy is flowing from the hot side
to the cold side.

hot heat cold

26 °C 26 °C

No net heat flow

The two purple objects are at the same temp and, therefore are in thermal
equilibrium. There is no net flow of heat energy here.
Temperature and Zeroth Law of Thermodynamics

• The zeroth law of thermodynamics: If two bodies are in thermal equilibrium


with a third body, they are also in thermal equilibrium with each other.
• By replacing the third body with a thermometer, the zeroth law can be
restated as two bodies are in thermal equilibrium if both have the same
temperature reading even if they are not in contact.

Two bodies reaching thermal


equilibrium after being
brought into contact in an
isolated enclosure.

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The Zeroth Law of Thermodynamics
We have already discussed the zeroth law, and
include it here for completeness:
If object A is in thermal equilibrium with object
C, and object B is separately in thermal
equilibrium with object C, then objects A and B
will be in thermal equilibrium if they are placed
in thermal contact.
Temperature Scales
• All temperature scales are based on some easily
reproducible states such as the freezing and boiling
points of water: the ice point and the steam point.

• Ice point: A mixture of ice and water that is in


equilibrium at 1 atm pressure (0°C or 32°F).

• Steam point: A mixture of liquid water and water


vapor (with no air) in equilibrium at 1 atm pressure
(100°C or 212°F).

• Celsius scale: in SI unit system


• Fahrenheit scale: in English unit system

• Thermodynamic temperature scale: A temperature


scale that is independent of the properties of any
substance.
• Kelvin scale (SI) Rankine scale (E)
• A temperature scale nearly identical to the Kelvin
scale is the ideal-gas temperature scale.

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Pressure
Pressure: A normal force exerted by a
fluid per unit area

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Equation of state
 An equation of state (EOS) is a thermodynamic expression
that relates pressure (P), temperature (T), and volume
(V). ... Many attempts have been made to describe the
thermodynamic behavior of fluids to predict their physical
properties at given conditions.
Boyle’s law & Charles law
 Boyle's law
 Boyle noted that the gas volume varied inversely with the pressure. In
mathematical form, this can be stated as:

 Charles's law
 In 1787 Jacques Charles indicated a linear relationship between volume and
temperature:
Ideal gas law

 The ideal gas law is the equation of state of a hypothetical ideal


gas. It is a good approximation to the behavior of many gases
under many conditions. The ideal gas law is often introduced in
its common form:

 where P is the absolute pressure of the gas, V is the volume of the gas, n is the
amount of substance of gas (measured in moles), T is the absolute temperature of
the gas and R is the ideal, or universal, gas constant.
 In SI units, P is measured in Pascal, V is measured in cubic meters, n is measured
in moles, and T in Kelvin (273.15 Kelvin = 0 degrees Celsius). R has the value 8.314
J·K−1·mol−1 or 0.08206 L·atm·mol−1·K−1 if using pressure in standard atmospheres
(atm) instead of Pascal, and volume in liters instead of cubic meters .
Molar form

 By replacing n with m / M, and subsequently introducing density


ρ = m/V, we get:
Ideal Gas Equation
Application to thermodynamic processes

 A thermodynamic process is defined as a system that moves from state 1 to


state 2. As shown in the first column of the table, basic thermodynamic
processes are defined such that one of the gas properties (P, V, T) is constant
throughout the process.
 In the final three columns, the properties (P, V, or T) at state 2 can be
calculated from the properties at state 1 using the equations listed.
Process Constant Known ratio P2 V2 T2

Isobaric process Pressure V2/V1 P2 = P 1 V2 = V1(V2/V1) T2 =


T1(V2/V1)

T2/T1 P2 = P 1 V2 = V1(T2/T1) T2 =
T1(T2/T1)

Isochoric process Volume P2/P1 P2 = P1(P2/P1) V2 = V1 T2 =


T1(P2/P1)

T2/T1 P2 = P1(T2/T1) V2 = V1 T2 =
T1(T2/T1)

Isothermal process Temperature P2/P1 P2 = P1(P2/P1) V2 = V1/(P2/P1) T2 = T1

V2/V1 P2 = P1/(V2/V1) V2 = V1(V2/V1) T2 = T1


Work
Work is a Mechanical form of Energy: e.g. Raising Piston,

Work  Force  Distance


dW  F  x
∆X
Force F
p 
Area x 2 Force

dW  pdV
Work
 Work is the energy transferred
between a system and
environment when a net force acts
on the system over a distance.
 Work is positive when the force is
in the direction of motion.
 Work is negative when the force is
opposite to the
motion.
Heat
• The energy transferred in a thermal interaction is called heat.
• The symbol for heat is Q.
• The energy equation now becomes
ΔEsys = ΔEmech + ΔEth = Wext + Q

Quick quiz: A gas cylinder and piston are covered with heavy insulation. The piston is
pushed into the cylinder, compressing the gas. In the process. The gas temperature

• Increases
• Decreases
• Doesn’t change
Heat and Thermal interactions
Distinguish between Heat, Temperature, and Thermal
energy
 Thermal energy is an energy of the system due to the motion of its
atoms and molecules. Thermal energy is a state variable, it may
change during a process. The system’s thermal energy continues to
exist even if the system is isolated and not interacting thermally with
its environment

 Heat is energy transferred between the system and the environment


as they interact. Heat is not a particular form of energy, nor is it a
state variable. Heat may cause the system’s thermal energy to
change, but that does not mean that heat and thermal energy are the
same thing.

 Temperature is a state variable, it is related to the thermal energy per


molecule. But not the same thing.
Internal Energy
Internal energy (also called thermal energy) is the energy an object or substance is due
to the kinetic and potential energies associated with the random motions of all the
particles that make it up. The kinetic energy is, of course, due to the motion of the
particles. To understand the potential energy, imagine a solid in which all of its
molecules are bound to its neighbors by springs. As the molecules vibrate, the springs
are compressed and stretched.

The hotter something is, the faster its molecules are


moving or vibrating, and the higher its temperature.
Temperature is proportional to the average kinetic energy
of the atoms or molecules that make up a substance.
Internal Energy
Internal Energy vs. Heat
The term heat refers is the energy that is transferred from one body or location
due to a difference in temperature. This is similar to the idea of work, which is
the energy that is transferred from one body to another due to forces that act
between them. Heat is internal energy when it is transferred between bodies.

Technically, a hot potato does not possess heat; rather it possesses


a good deal of internal energy on account of the motion of its molecules. If that
potato is dropped in a bowl of cold water, we can talk about heat: There is a heat
flow (energy transfer) from the hot potato to the cold water; the potato’s internal
energy is decreased, while the water’s is increased by the same amount.
Temperature vs. Internal Energy

Temperature and internal energy are related but not the same thing. Temperature is directly
proportional to the average molecular kinetic energy.

Consider a bucket of hot water and a swimming pool full of cold water. The hot water is
at a higher temperature, but the pool water actually has more internal energy! This is
because, even though the average kinetic energy of the water molecules in the bucket is
much greater than that of the pool, there are thousands of times more molecules in the
pool, so their total energy is greater.
First Law of Thermodynamics
Energy is always conserved. It can change forms: kinetic, potential,
internal etc., but the total energy is a constant. Another way to say it is
that the change in thermal energy of a system is equal to the sum of the
work done on it and the amount of heat energy transferred to it.
PdV Work
Area A Let the Piston be moving from Thermodynamic

P2 V2 Equilibrium State 1 (P1, V1) to State 2 (P2, V2).


P1 V1 Let the values at any intermediate Equilibrium
State is given by P and V.

State 1 State 2

For a small displacement, dL, the small Work done is;


P1
dW = F * dL = P*A*dL = PdV
Quasi-Static
Similarly, for Process 1 – 2; we can say that;

Pressure
Process Path
V2 P2
W1 2   PdV
V1
V1 Volume
V2
PdV Work
• Isobaric Process P=Const
Isobaric
State 1 State 2
V2

Pressure (P)
W1 2   PdV  P (V2  V1 )
V1 W1-2

Volume (V) V2
V1
• An isobaric process is a constant pressure process. ΔU, W, and Q are generally non-zero, but calculating the work
done by an ideal gas is straightforward
W = P·ΔV
• Water boiling in a saucepan is an example of an isobar process
PdV Work
State 1
P1
V=Const
Pressure (P)

Isochoric
• Isochoric Process

V2

W1 2   PdV  0
V1

P2 State 2

Volume (V)

• An isochoric process is a constant volume process. When the volume of a


system doesn’t change, it will do no work on its surroundings. W = 0
ΔU = Q
• Heating gas in a closed container is an isochoric process
PdV Work
Isothermal Process:
V2

P1
State 1
W1 2   PdV
PV = C V1
Pressure

Quasi-Static
P1V1
PV  P1V1  C  P 
V
State 2 V2
dV V2 P1
P2 W1 2  P1V1   P1V1 ln  P1V1 ln
V1
V V1 P2
V1 Volume V2

 An isothermal process is a constant temperature process. Any heat flow into or out of the system
must be slow enough to maintain thermal equilibrium
 For ideal gases, if ΔT is zero, ΔU = 0
 Therefore, Q = W. Any energy entering the system (Q) must leave as work (W)
PdV Work
n
n n PV
PV  P1V1  P2V2
n
 C  P  1 n1
1 V
P1 PVn = C V2

W1 2   PdV
Pressure

V1

V2 V2
n dV  V  n 1 
  P1V1
n
W1 2  P V  
n =∞ n =1 V1
Vn
1 1
  n  1 V1
2
P2
 
n n 1 n n 1 n
PV 1 n 1 n P V X V2  P1V1 X V1
n =3 n =2  1 1 V2  V1  2 2
1 n 1 n
P1V1   P2  
n 1 / n
Volume P1V1  P2V2
  1    
n 1 n  1   P1  

 An adiabatic process transfers no heat


therefore Q = 0
 ΔU = Q – W
 When a system expands adiabatically, W is positive (the system does work) so ΔU is negative.
 When a system compresses adiabatically, W is negative (work is done on the system) so ΔU is positive.
Specific Heat

DEFINITION :
m = 1 kg
∆T = 1 ºC The Energy required to raise the temperature of a unit
Sp. Heat = 5 kJ/kg ºC mass of a substance by 1 degree.

5 kJ

Specific Heat at Constant Pressure (CP) :

The Energy required to raise the temperature of a unit mass of a substance by 1 degree, as the
Pressure is maintained CONSTANT.

Specific Heat at Constant Volume (CV) :

The Energy required to raise the temperature of a unit mass of a substance by 1 degree, as the
Volume is maintained CONSTANT.
Specific heat
Specific heat at constant volume Cv

Hence, CV is change in Internal Energy


of a substance per unit change in
temperature at constant Volume.
Specific Heat at constant Pressure

Hence, CP is change in Enthalpy of a substance


per unit change in temperature at constant
Pressure.
Relation between Specific Heat
The End

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