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Thermodynamics

Measured Thermodynamics
Properties and Basic Concept
Thermodynamics System
Surroundings

System Boundary

• Open system  Mass and energy can flow across boundary


• Closed system  Mass cannot flow across boundary BUT energy still can flow across boundary
• Isolated systesm  Both mass and energy cannot flow across boundary
Properties
Intensive Extensive
Does not depend on the amount of Depends on the amount of material
material
Temperature Volume
Pressure Enthalpy
Density Internal Energy
Specific volume Mass
If I add material
Google it yourself  Google it yourself  twice of the
initial amount
Intensive Form Extensive Form would the
property change
Density Mass twice of its initial
amount?
Specific Volume Volume
Specific Enthalpy Enthalpy
Specific Internal Energy Internal Energy
Specific Entropy Entropy
Google it yourself  Google it yourself 
Thermodynamics Properties
• DOES NOT depend on how system undergoes the process
• DEPENDS on the initial and final state

We could create hypothetical paths


Common Terms in Thermodynamics Process
• Adiabatic  No heat transfer (Q)
• Isothermal  Constant temperature
• Isobaric  Constant pressure
Equation of state?
• Isochoric  Constant volume
• State function  properties that does not depend on how system
undergoes process ; thermodynamic properties (P, T, v)
• Path function  properties that depends on how the system
undergoes process (Q and W)
Equilibrium
• Equilibrium refers to a condition in which the state neither changes
with time nor has a tendency to spontaneously change.
• For a system to be in equilibrium there must be no net change in the
system and surroundings.
• At equilibrium there is no net driving force, both in the system and in
the surroundings. Any changes in each side will cause energy or mass
flow through boundary.
• If the equilibrium state is stable, the system will return to that state
when a small disturbance is imposed upon it.
• It can only occurs in closed system.
Equilibrium.. again
Types of equilibrium

Mechanical Equilibrium There is no pressure difference


(P system = P surrounding)
Thermal Equilibrium There is no temperature difference
(T system = T surrounding)
Chemical Equilibrium There is no tendency for chemical
substance to undergo phase change
Equilibrium or Steady State?

• Are equilibrium and steady state the same thing?


• Nope.
• If a system is in equilibrium state then it is in a steady state
• But the reverse is not true. Why?
• Logic. If p  q we cannot say If q  p. Haha. Kidding. But it’s true tho.
• There will always be a net driving force when the mass enter or exit the system. Moreover,
although the system may not undergoes change in time, the material that enters and exits the
system will always undergoes changes. It means there will be a net change in the surrounding.
State Postulate of Pure Substance
• Thermodynamics properties (P, T, v) determine the state of a system
• State Postulate says:
If we have a system containing a pure substance, its thermodynamic
state and, therefore, all its intensive thermodynamic properties can be
determined from two independent intensive properties.
• v(P,T) ; P(v,T) ; T(P,v)
Gibbs Phase Rule
• How do I know how many independent variables that I need to
determine a system state?

• m=the number of chemical substance in the system


• Π=the number of phases
Lil practice

• When we have two phases present, Mr. Gibbs says we only need one property to determine the
state for each phase.
• But, the pressure and temperature are the same for each phases . Did you know that
thermodynamics properties may differ for each phases?
• We need quality (x) to constraint the properties for each phase
I know you are confused. Why tiba tiba muncul x sih? On the board guys 
PvT Diagram
Change of State
Saturation Vapor vs Vapor Pressure
• Are saturation vapor and vapor pressure the same?
• Nope.
• The saturation pressure is the pressure at which a pure substance boils at a given temperature.
• The vapor pressure of a substance, is its contribution to the total pressure in a mixture at a given
temperature. This contribution is equal to the partial pressure of the substance in an ideal gas mixture.
Exercise
1. Gas in a cylinder undergoes a change where its volume is halved.
Assume the gas is an ideal gas and temperature remains constant.
What changes will it have on the pressure?
2. Are you sure pressure is an intensive properties?
3. Consider a two-phase system at a specified T that contains 20%
vapor, by mass, and 80% liquid. Identify the state on a Tv phase
diagram.

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