9/16/2013

Properties of Pure Substances

Now well start to learn how temperature, volume, and pressure are related for a pure substance. Well also learn the conditions for phase change, and how we can use diagrams understand these phenomena. - Pure substance (5) - Saturation temperature and pressure (3) - Property diagrams (7)

G. Bramesfeld

AER 309 Thermodynamics

v 1.0

Ryerson University

Pure substance (1)

A pure substance is one that has a fixed chemical composition throughout. Air is a mixture of several gases, but it is considered to be a pure substance

Nitrogen and gaseous air are pure substances.

A mixture of liquid and gaseous water is a pure substance (everything is still only water), but a mixture of liquid and gaseous air is not (liquid air and gaseous air have different enough chemistry).

G. Bramesfeld

AER 309 Thermodynamics

v 1.0

Ryerson University

9/16/2013

Pure substance (2)

All pure substances can occur in various phases if exposed to the right conditions.

The molecules in a solid are kept at their positions by the large springlike inter-molecular forces. In a solid, these attractive and repulsive forces tend to maintain the molecules at relatively constant distances from each other.

The arrangement of atoms in different phases: (a) molecules are at relatively fixed positions in a solid (b) groups of molecules move about each other in the liquid phase (c) molecules move about at random in the gas phase
G. Bramesfeld AER 309 Thermodynamics v 1.0 Ryerson University

Pure substance (3)

Most pure substances can go through five different states if the conditions are right. Well look at pure water to illustrate these stages.

At 1 atm and 20oC, water exists in a liquid phase called compressed liquid, otherwise known as subcooled liquid, where the substance is not close to vapourizing.

Increasing the temperature to 100oC at 1 atm, water exists as a liquid that is ready to vapourize, and we call this a saturated liquid.
G. Bramesfeld AER 309 Thermodynamics v 1.0 Ryerson University

9/16/2013

Pure substance (4)

As more heat is transferred, part of the saturated liquid vapourizes the molecules get so excited that they break off from the liquid and enter the vapour (gas) state. The water is then a saturated liquid-vapour mixture, a state where the liquid and vapour phases coexist in equilibrium.

At 1 atm pressure, the temperature remains constant at 100C until the last drop of liquid is vaporized this state is called a saturated vapour.

As more heat is transferred, the temperature of the vapour starts to rise, and we call this state a superheated vapour; this state is not about to condense, i.e. is not near a saturated vapour.
G. Bramesfeld AER 309 Thermodynamics v 1.0 Ryerson University

Pure substance (5)

If the entire process between state 1 and 5 described in the figure is reversed by cooling the water while maintaining the pressure at the same value, the water will go back to state 1, retracing the same path, and in so doing, the amount of heat released will exactly match the amount of heat added during the heating process.

T-v diagram for the heating process of water at constant pressure. Remember: v is the specific volume
G. Bramesfeld AER 309 Thermodynamics v 1.0 Ryerson University

9/16/2013

Saturation temperature and pressure (1)

The temperature at which water starts boiling depends on the pressure; therefore, if the pressure is fixed (held constant), so is the boiling temperature. We call the linked temperature and pressure at which phase change occurs the saturation temperature and saturation pressure. Pure water boils at 100oC and 1 atm pressure. Saturation temperature Tsat: the temperature at which a pure substance changes phase at a given pressure Saturation pressure Psat: the pressure at which a pure substance changes phase at a given temperature

The liquidvapor saturation curve of a pure substance (numerical values are for water).

G. Bramesfeld

AER 309 Thermodynamics

v 1.0

Ryerson University

Saturation temperature and pressure (2)

Latent heat: the amount of energy absorbed or released during a phase-change process Latent heat of fusion: the amount of energy absorbed during melting, which is equivalent to the amount of energy released during freezing Latent heat of vapourization: the amount of energy absorbed during vaporization, and it is equivalent to the amount of energy released during condensation (swamp cooler) The magnitudes of the latent heats depend on the temperature or pressure at which phase change occurs

At 1 atm pressure, the latent heat of fusion of water is 333.7 kJ/kg, and the latent heat of vaporization is 2256.5 kJ/kg
The atmospheric pressure, and thus the boiling temperature of water, decreases with elevation
G. Bramesfeld AER 309 Thermodynamics v 1.0 Ryerson University

9/16/2013

Saturation temperature and pressure (3)

Some examples of Tsat and Psat dependence: The evaporating water at atmospheric pressure keeps the temperature at about 100C, thus below the ignition temperature of the paper.

The temperature of liquid nitrogen exposed to the atmosphere remains constant at -196C, and thus it maintains the test chamber at -196C.
G. Bramesfeld AER 309 Thermodynamics

In 1775, ice was made by evacuating the air space in a water tank.
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Property diagrams (1)

The variations of properties during phase-change processes are best studied and understood with the help of property diagrams such as the T-v, P-v, and P-T diagrams for pure substances.

T-v diagram of constant-pressure phase-change processes of a pure substance at various pressures (numerical values are for water).

G. Bramesfeld

AER 309 Thermodynamics

v 1.0

Ryerson University

9/16/2013

Property diagrams (2)

There are several important lines and regions to notice on a T-v diagram, including the dome shape and constant pressure lines. saturated liquid line saturated vapor line compressed liquid region superheated vapor region saturated liquidvapor mixture region (wet region)

T-v diagram of a pure substance.

At supercritical pressures (P > Pcr), there is no distinct phase-change (boiling) process. The critical point is the point at which the saturated liquid and saturated vapor states are identical.
G. Bramesfeld AER 309 Thermodynamics v 1.0 Ryerson University

Property diagrams (3)

We can also look at P-v diagrams, which also have a dome, but this time we have constant temperature lines.

P-v diagram of a pure substance.

The pressure in a pistoncylinder device can be reduced by reducing the weight of the piston, or the temperature reduced by decreasing the amount of heat added to the system.
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G. Bramesfeld

AER 309 Thermodynamics

9/16/2013

Property diagrams (4)

But what about the solid phase? The P-v diagram depends on whether or not the substance contracts or expands upon freezing.

P-v diagram of a substance that contracts on freezing.

P-v diagram of a substance that expands on freezing (such as water).

At triple-point pressure and temperature, a substance exists in three phases in equilibrium. For water, this point is at a temperature Ttp=0.01oC and a pressure Ptp=0.6117 kPa.
G. Bramesfeld AER 309 Thermodynamics v 1.0 Ryerson University

Property diagrams (5)

Some substances can phase change from the solid phase to the vapor phase directly, without passing through a liquid phase. This is called sublimation.

At low pressures (below the triple-point value), solids evaporate without melting first (sublimation).

P-T phase diagram of pure substances.

G. Bramesfeld

AER 309 Thermodynamics

v 1.0

Ryerson University

9/16/2013

Property diagrams (6)

We can also combine two-dimensional diagrams to form three-dimensional surfaces, such as the P-v-T surfaces shown below which present a great deal of information at once. However, in a thermodynamic analysis it is more convenient to work with two-dimensional diagrams, such as the P-v and T-v diagrams.

P-v-T surface of a substance that contracts on freezing.

G. Bramesfeld AER 309 Thermodynamics v 1.0

P-v-T surface of a substance that expands on freezing (like water).

Ryerson University

Summary Property Diagrams (7)

State Principle: Only a fixed number of thermodynamic intensive properties are independent of one another. Experimental evidence suggests that the maximum number of independent properties is two. For example: ideal gas: =

For any simple compressible material (such as water) wee can develop either a property relation or tables to show p- p--T relationship. If we plot this relationship, we can illustrate this as a p--T surface. Commonly used names for the states near the vapour dome are sub-cooled or compressed liquid (, to left of vapour dome) saturated liquid saturated vapour Superheated vapour (to right of dome)

G. Bramesfeld

AER 309 Thermodynamics

v 1.0

Ryerson University