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Thermodynamics Pure Substance

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Pure Substance

A substance with a fixed chemical composition throughout e.g. water, N2, CO2 etc. A single-phase mixture of various elements or compounds can be treated as a pure substance as long as the mixture is homogeneous throughout, air is the most important example A mixture of two or more phases is a pure substance as long as the chemical composition for each phase is the same e.g. ice-water mixture, water-vapor mixture

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Phase Diagram Substance that contracts on Freezing

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Phase Diagram Substance that expands on Freezing

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Physical State & Phase Change


The potential energy between the particlesmolecules, atoms or ions in a sample of matter results from attractive and repulsive forces called interparticle forces, or, more commonly , intermolecular forces. The interplay between these forces and the kinetic energy of the particles give rise to the properties of each state (or phase) and to phase change, the changes from one phase to another Intramolecular forces (bonding forces): exist within each molecule (or polyatomic ion) and influences the chemical properties of the substance. Intermolecular forces: exist between the molecules (or ions) and influences the physical properties of the substance.
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Phase
Three common phases: solids, liquids and gases Solids: molecules closely packed, high molecular forces, definite shape and volume Liquids: molecules less closely packed, weaker molecular forces, fluid shape and definite volume Gases: molecules move around, weakest molecular forces, no shape and container-defined volume Other states of matter that we will not discuss: plasmas, Bose-Einstein condensates,
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Physical States
Gas: the energy of attraction is small relative to the energy of motion: so, on average, the particles are far apart. A gas moves randomly throughout its container and fills it. Liquid: the attraction are stronger because the particles are in virtual contact. But their kinetic energy still allows them to tumble randomly over and around each other. Liquid conform to the shape of its container but has surface. With very little free space between the particles, liquids flow and diffuse but much more slowly than gases. Solid: the attraction dominates the motion to such an extent that the particle remain in position relative to one another, jiggling in place. A solid has a specific shape. Consequently, solids compress even less than liquids, and their particles do not flow significantly.
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Phase Change
Molecular motion determined by temperature Higher temperatures result in higher microscopic internal energy (translational, rotational, vibrational) Energy content increases from solids to liquids to gases Phase change processes important in many practical applications e.g. boiler and condenser (liquid-vapor equilibrium) in steam power plant cycle In general, liquid-vapor phase changes will be of the most importance for this class

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Type of Phase Change


Condensation: the process by which a gas changes into a liquid. Vaporization: changing from liquid into gas. Freezing: changing from liquid to solid. Melting (fusion): the process by which a solid changes into liquid. Sublimation: when a solid changes to gas without becoming liquid. Deposition: gas changing to solid without becoming liquid.

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Phase Change

GAS

A: Melting
D C Energy (Enthalpy)
LIQUID

B: Freezing C: Vaporization D: Condensation E: Sublimation F: Deposition

E A B
SOLID

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T-v Diagram: Heating at Constant P


1: Sub-Cooled Liquid (Compressed Liquid) 2: Saturated Liquid
5 2 1
V
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3: Saturated LiquidVapor Mixture 4: Saturated Vapor 5: Superheated Vapor

Critical Point

Saturated liquid 2-phase Saturated vapor

T-v Diagram (contd.)

Sub-Cooled Liquid: liquid too cold to vaporize at the given pressure Saturated Liquid: liquid about to vaporize Saturated Liquid-Vapor Mixture: liquid and vapor co-exist in equilibrium Saturated Vapor: vapor about to condense Superheated Vapor: vapor too hot to condense at the given pressure

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Saturation T & P

Saturation Temperature (Tsat): At a given pressure, the temperature at which a pure substance changes phase from liquid to vapor or vapor to liquid Saturation Pressure (Psat): At a given temperature, the pressure at which the given pure substance changes phase from liquid to vapor or vapor to liquid Tsat = f(Psat) or Psat = g(Tsat) Tsat increases with Psat and vice-versa

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Critical Point

Critical Point: A point on the phase change diagram of the given pure substance where saturated liquid and saturated vapor states are identical Beyond the critical point, no distinct phase change process For water, Pcr ~ 221 bar; Tcr ~ 374.1C At critical pressure, no separation between sub-cooled liquid and superheated vapor, i.e., the two-phase region is non-existent

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P-V Diagram
p

v
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T-v and P-v Diagrams


T 1 3 P2 > P1 P2 P1

On a T-v diagram, lines of constant pressure

Saturated Vapor Line Saturated Liquid Line

P
Critical Point

T2 > T1

1
V

T2

3
Saturated Vapor Line

T1

On a P-v diagram, lines of constant temperature


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Saturated Liquid Line

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Triple point
All three phases (S, L and V) exist in equilibrium

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P-v-T Surface

For water, triple point is defined at 0.01C at a pressure of 0.6113 kPa In three dimensional space, we can indicate relationships between P, v and T for a given pure substance on P-v-T surface T-v, P-v and P-T diagrams are simply projections from this surface P-v-T surface depicts the complete behavior of a given pure substance

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