Thermodynamics I

1. 2. 3. 4. 5. 6. 7. 8. Introduction Basic Concepts of Thermodynamics Energy, Energy Transfer, and General Energy Analysis Properties of Pure Substances Energy Analysis of Closed Systems Energy and Mass Analysis of Control Volumes The Second Law of Thermodynamics Entropy Steam Power Cycle Applications Examples

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Overview Properties of Pure Substances

3-1 3-2 3-3 3-4 3-5 3-6 3-7 Pure Substance Phases of a Pure Substance Phase-Change Processes of Pure Substances Property Diagrams for Phase-Change Processes Property Tables The Ideal-Gas Equation of State Compressibility Factor

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Pure Substance
A pure substance has a fixed chemical composition throughout various processes. Examples are: water, nitrogen, helium and carbon dioxide. Homogeneous mixtures also qualify as pure substances (e.g. air). A mixture of two or more phases can still be a pure substance.

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Phases of a Pure Substance

3 principal phases: solid, liquid and gas-phase. Substances may have several phases with the principal phase (e.g. ice has 7, iron has 3, carbon has 2).

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Phase-Change Processes
Saturated Liquid Saturated LiquidVapour Mixture

Superheated Vapour

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Property Diagrams for PhaseChange Processes: T-v

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Property Diagrams for PhaseChange Processes: P-v

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Rankine Cycle - Phase Change

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Saturation Temperature and Saturation Pressure

The temperature at which water starts boiling depends on the pressure. If the pressure is fixed, so is the boiling temperature. During the phase change the two phases are in equilibrium. For a pure substance and a given pressure the phase-change temperature is called saturation temperature Tsat. For a pure substance and a given temperature the phase-change pressure is called saturation pressure Psat.

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Some Consequences of Tsat and Psat Dependence

The temperature of liquid nitrogen exposed to the atmosphere remains constant at 196C, and thus it maintains the test chamber at 196C.
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In 1775, ice was made by evacuating the air space in a water tank.
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P-v Diagram for Substance that Contracts/Expands on Freezing

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P-T or Phase Diagram

Latent heat of fusion

Latent heat of vaporization/ condensation

Latent heat of sublimation/ deposition

Substance Water Nitrogen

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Ttp (K) 273.16 63.18

Ptp (kPa) 0.61 12.6

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Enthalpy
Enthalpy is a combination property. In the analysis of cycles we frequently encounter the expression: U+PV For simplicity reason this quantity is termed enthalpy: H=U+PV (kJ) h=u+Pv (kJ/kg)

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Saturated Liquid and Vapour States

= vg v f v fg = ug u f u fg = hg h f h fg = sg s f s fg

vf
vf: specific volume of saturated liquid
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vg
vg: specific volume of saturated vapour
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Saturated Liquid and Vapour States

Example A rigid tank contains 50 kg of saturated liquid water at 90C. Determine the pressure in the tank and the volume of the tank.

Answer: P=70.18kPa V=0.0518m3

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Saturated Liquid and Vapour States

Example A mass of 200g of saturated liquid water is completely vaporized at a constant pressure of 100kPa. Determine a) the volume change and b) the amount of energy added to the water.

Answer: DV=0.3386m3 DE=451.6kJ

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Saturated Liquid-Vapour Mixtures Quality x

To analyse a liquid-vapour mixture in the wet-region we need to know the proportions of the liquid and the vapour phases. The new property is called quality x:

x=

mvapour mtotal

: mass fraction of vapour

mliquid : mass fraction of liquid (or simply moisture) 1 x = mtotal mliquid + mvapour = m f + mg where mtotal =
= V f + Vg V m mg mg = = =x 1 x and mv = m f v f + mg vg using m m m v = v f + xv fg (1 x)v f + xvg or v = mf
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Saturated Liquid-Vapour Mixtures Quality x

x= v vf v fg

= v v f + xv fg = u u f + xu fg = h h f + xh fg = s s f + xs fg

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Saturated Liquid-Vapour Mixtures

Example A rigid tank contains 10 kg of saturated liquid water at 90C. If 8 kg of the water is in the liquid phase and the rest is in the vapour phase, determine a) the pressure in the tank, and b) the volume of the tank.

Answer: P=70.18kPa V=4.73m3

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Saturated Liquid-Vapour Mixtures

Example An 80 L vessel contains 4 kg of refrigerant 134-a at a pressure of 160kPa. Determine a) the temperature of refrigerant, b) the quality, c) the enthalpy of the refrigerant, and d) the volume occupied by the vapour phase. Answer: T=Tsat@kPa=-15.60C x=0.158 h=62.7kJ/kg mg=0.632kg and Vg=0.0777m3
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Compressed Liquid
A compressed liquid is to be approximated as saturated liquid at the given temperature. The properties depend more on the temperature than they do on the pressure.

Example: Determine the internal energy of compressed liquid water at 80C and 5 MPa: From compressed liquid table: u=333.72kJ/kg From saturation table: u334.86kJ/kg Error: 0.34%

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Superheated Vapour
Pressure and Temperature are no longer dependent variables. Super-heated vapour is a single-phase substance.

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Superheated Vapour
Example Determine the temperature of water at a state of P=0.5MPa and h=2890kJ/kg. Answer: At 0.5MPa saturated vapour: hg=2748.7kJ/kg. Therefore we have superheated vapour. Linear interpolation from tables gives: T=216.4C

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 Equation of state: Any equation that relates the pressure, temperature, and specific volume of a substance. The simplest and best-known equation of state for substances in the gas phase is the ideal-gas equation of state. This equation predicts the P-v-T behavior of a gas quite accurately within some properly selected region.

THE IDEAL-GAS EQUATION OF STATE

Ideal gas equation of state P: absolute pressure T: absolute temperature in Kelvin

R: gas constant M: molar mass (kg/kmol) Ru: universal gas constant

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THE IDEAL-GAS EQUATION OF STATE

Different substances have different gas constants.

Ideal gas equation at two states for a fixed mass

Various expressions of ideal gas equation

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Compressibility Factor
The compressibility factor Z is a correction factor and is a measure of the deviation from ideal-gas behaviour. Z is defined as:

Pv Z= RT Pv = ZRT or vactual Z= videal

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