Page 1
Properties of pure substances
Properties of Pure Substance
• A pure substance is a material with homogeneous and invariable
composition.
• Pure substances can have multiple phases, an ice water mixture is still a pure
substance but an air-steam is not a pure substance.
Pure Substance:
• A substance that has a fixed chemical composition throughout is called a
pure substance i.e., water, nitrogen, helium, and CO2.
• Substances which are mixture of various elements or compounds also
qualifies as pure substances as long as mixture is homogeneous.
Vapour Vapour
Liquid Liquid
(a) H2 0 (b) Air
Saturation Temperature and Saturation Pressure:
• At given pressure, the temperature at which a pure substance changes phase
is called the saturation temperature Tsat.
• Likewise at a given temperature, the pressure at which a pure substance
changes phase is called the saturation pressure psat.
Page 2
Properties of pure substances
Properties of Pure Substance
• A pure substance is a material with homogeneous and invariable
composition.
• Pure substances can have multiple phases, an ice water mixture is still a pure
substance but an air-steam is not a pure substance.
Pure Substance:
• A substance that has a fixed chemical composition throughout is called a
pure substance i.e., water, nitrogen, helium, and CO2.
• Substances which are mixture of various elements or compounds also
qualifies as pure substances as long as mixture is homogeneous.
Vapour Vapour
Liquid Liquid
(a) H2 0 (b) Air
Saturation Temperature and Saturation Pressure:
• At given pressure, the temperature at which a pure substance changes phase
is called the saturation temperature Tsat.
• Likewise at a given temperature, the pressure at which a pure substance
changes phase is called the saturation pressure psat.
Example: For water at a pressure of 101.325 kPa, Tsat is 100°C, conversely at a
temperature of 100°C, psat is 101.325 kPa.
Latent Heat:
• The amount of energy absorbed or released during a phase change process is
called the latent heat.
• The amount of energy absorbed during melting is called the latent heat of
vaporization.
• Similarly, the amount of energy absorbed during vaporization is called latent
heat of vaporization and is equivalent to the energy released during
condensation.
Liquid-Vapour Saturation Curve:
From the following figure, it is clear that Tsat increases with psat. Thus, a substance
at higher pressure will boil at higher temperatures.
Tsat = f(Psat)
^sat •
• In the kitchen, higher boiling temperature means shorter cooking time and
energy saving.
• The atmospheric pressure, and thus the boiling temperature of water,
decreases with elevation. Therefore, it takes longer time to cook at higher
altitudes than it does at sea level.
Property Diagrams for Phase-change Process
The T-V Diagram:
• Consider piston cylinder device containing liquid water at 20°C and 1 atm.
• Water will start boiling at a much higher temperature (179.9°C) at inside
pressure of the cylinder reaches at 1 MP.
• The specific volume of the saturated liquid is larger and the specific volume of
the saturated vapour is smaller than the corresponding values at 1 atm
pressure. That is, the horizontal line that connects the saturated liquid and
saturated vapour states is much shorter.
• As the pressure is increased further, this saturation line will continue to get
shorter as shown in figure and it will become a point when the pressure
reaches 22.09 MPa for the case of water. This point is called the critical point
Page 3
Properties of pure substances
Properties of Pure Substance
• A pure substance is a material with homogeneous and invariable
composition.
• Pure substances can have multiple phases, an ice water mixture is still a pure
substance but an air-steam is not a pure substance.
Pure Substance:
• A substance that has a fixed chemical composition throughout is called a
pure substance i.e., water, nitrogen, helium, and CO2.
• Substances which are mixture of various elements or compounds also
qualifies as pure substances as long as mixture is homogeneous.
Vapour Vapour
Liquid Liquid
(a) H2 0 (b) Air
Saturation Temperature and Saturation Pressure:
• At given pressure, the temperature at which a pure substance changes phase
is called the saturation temperature Tsat.
• Likewise at a given temperature, the pressure at which a pure substance
changes phase is called the saturation pressure psat.
Example: For water at a pressure of 101.325 kPa, Tsat is 100°C, conversely at a
temperature of 100°C, psat is 101.325 kPa.
Latent Heat:
• The amount of energy absorbed or released during a phase change process is
called the latent heat.
• The amount of energy absorbed during melting is called the latent heat of
vaporization.
• Similarly, the amount of energy absorbed during vaporization is called latent
heat of vaporization and is equivalent to the energy released during
condensation.
Liquid-Vapour Saturation Curve:
From the following figure, it is clear that Tsat increases with psat. Thus, a substance
at higher pressure will boil at higher temperatures.
Tsat = f(Psat)
^sat •
• In the kitchen, higher boiling temperature means shorter cooking time and
energy saving.
• The atmospheric pressure, and thus the boiling temperature of water,
decreases with elevation. Therefore, it takes longer time to cook at higher
altitudes than it does at sea level.
Property Diagrams for Phase-change Process
The T-V Diagram:
• Consider piston cylinder device containing liquid water at 20°C and 1 atm.
• Water will start boiling at a much higher temperature (179.9°C) at inside
pressure of the cylinder reaches at 1 MP.
• The specific volume of the saturated liquid is larger and the specific volume of
the saturated vapour is smaller than the corresponding values at 1 atm
pressure. That is, the horizontal line that connects the saturated liquid and
saturated vapour states is much shorter.
• As the pressure is increased further, this saturation line will continue to get
shorter as shown in figure and it will become a point when the pressure
reaches 22.09 MPa for the case of water. This point is called the critical point
and it is defined as the point at which the saturated liquid and saturated
vapour state are identical.
• At pressure above the critical pressure, there will not be a distinct phase
change. Instead, the specific volume of the substance will continually
increase and at all times there will be only one phase present. It is customary
to refer to the substance as superheated vapour at temperature above the
critical temperature and as compressed liquid at temperatures below the
critical temperature.
T V diagram of constant pressure phase-change process of a
pure substances at various pressures.
The p-V Diagram:
• The general shape of the p-V diagram of a pure substance is very much like
the T-V diagram but the T = constant lines on this diagram have a downward
trend.
• Consider again a piston cylinder device that contains liquid water at 1 MPa
and 150°C, water at this state exists as a compressed liquid. Now, the weights
on top of the piston are removed one by one so that the pressure inside the
cylinder decreases gradually.
• The water is allowed to exchange heat with the surroundings so its
temperature remains constant.
• As the pressure decreases, the volume of the water will increase slightly,
when the pressure reaches the saturation pressure volume at the specific
temperature, the water will start to boil.
• During this vaporisation process, both the temperature and the pressure
remain constant but the specific volume increases. Once the last drop of
liquid is vaporised further reduction in pressure results in a further increase in
specific volume.
• If the process is repeated for other temperatures similar paths will be
obtained for the phase change processes.
Triple Phase:
• When all three phases of a pure substance co-exist in equilibrium. It is called
triple phase.
• Triple phase states form a line called the triple line.
• The triple line appears as a point on the p-T diagram and therefore is often
called the triple point.
Page 4
Properties of pure substances
Properties of Pure Substance
• A pure substance is a material with homogeneous and invariable
composition.
• Pure substances can have multiple phases, an ice water mixture is still a pure
substance but an air-steam is not a pure substance.
Pure Substance:
• A substance that has a fixed chemical composition throughout is called a
pure substance i.e., water, nitrogen, helium, and CO2.
• Substances which are mixture of various elements or compounds also
qualifies as pure substances as long as mixture is homogeneous.
Vapour Vapour
Liquid Liquid
(a) H2 0 (b) Air
Saturation Temperature and Saturation Pressure:
• At given pressure, the temperature at which a pure substance changes phase
is called the saturation temperature Tsat.
• Likewise at a given temperature, the pressure at which a pure substance
changes phase is called the saturation pressure psat.
Example: For water at a pressure of 101.325 kPa, Tsat is 100°C, conversely at a
temperature of 100°C, psat is 101.325 kPa.
Latent Heat:
• The amount of energy absorbed or released during a phase change process is
called the latent heat.
• The amount of energy absorbed during melting is called the latent heat of
vaporization.
• Similarly, the amount of energy absorbed during vaporization is called latent
heat of vaporization and is equivalent to the energy released during
condensation.
Liquid-Vapour Saturation Curve:
From the following figure, it is clear that Tsat increases with psat. Thus, a substance
at higher pressure will boil at higher temperatures.
Tsat = f(Psat)
^sat •
• In the kitchen, higher boiling temperature means shorter cooking time and
energy saving.
• The atmospheric pressure, and thus the boiling temperature of water,
decreases with elevation. Therefore, it takes longer time to cook at higher
altitudes than it does at sea level.
Property Diagrams for Phase-change Process
The T-V Diagram:
• Consider piston cylinder device containing liquid water at 20°C and 1 atm.
• Water will start boiling at a much higher temperature (179.9°C) at inside
pressure of the cylinder reaches at 1 MP.
• The specific volume of the saturated liquid is larger and the specific volume of
the saturated vapour is smaller than the corresponding values at 1 atm
pressure. That is, the horizontal line that connects the saturated liquid and
saturated vapour states is much shorter.
• As the pressure is increased further, this saturation line will continue to get
shorter as shown in figure and it will become a point when the pressure
reaches 22.09 MPa for the case of water. This point is called the critical point
and it is defined as the point at which the saturated liquid and saturated
vapour state are identical.
• At pressure above the critical pressure, there will not be a distinct phase
change. Instead, the specific volume of the substance will continually
increase and at all times there will be only one phase present. It is customary
to refer to the substance as superheated vapour at temperature above the
critical temperature and as compressed liquid at temperatures below the
critical temperature.
T V diagram of constant pressure phase-change process of a
pure substances at various pressures.
The p-V Diagram:
• The general shape of the p-V diagram of a pure substance is very much like
the T-V diagram but the T = constant lines on this diagram have a downward
trend.
• Consider again a piston cylinder device that contains liquid water at 1 MPa
and 150°C, water at this state exists as a compressed liquid. Now, the weights
on top of the piston are removed one by one so that the pressure inside the
cylinder decreases gradually.
• The water is allowed to exchange heat with the surroundings so its
temperature remains constant.
• As the pressure decreases, the volume of the water will increase slightly,
when the pressure reaches the saturation pressure volume at the specific
temperature, the water will start to boil.
• During this vaporisation process, both the temperature and the pressure
remain constant but the specific volume increases. Once the last drop of
liquid is vaporised further reduction in pressure results in a further increase in
specific volume.
• If the process is repeated for other temperatures similar paths will be
obtained for the phase change processes.
Triple Phase:
• When all three phases of a pure substance co-exist in equilibrium. It is called
triple phase.
• Triple phase states form a line called the triple line.
• The triple line appears as a point on the p-T diagram and therefore is often
called the triple point.
p V diagram of pure substance
• No substance can exist in the liquid phase in stable equilibrium at pressure
below the triple point pressure.
• The same can be said for temperature for substance that contract on
freezing.
• Substances at high pressure can exist in the liquid phase at temperatures
below the triple point temperature.
The p-T Diagram:
• Solid - Liquid = Fusion
• Liquid - Vapour = Vaporisation
• Solid - Vapour = Sublimation
Substances that Substances that
expand on contract on
Enthalpy
• Enthalpy is a measure of the total energy of a thermodynamic system.
• It includes energy required to create a system and the amount of energy
required to make room for it by displacing its environment and establishing its
volume and pressure.
• For certain type of processes particularly in power generation and
refrigeration.
o Enthalpy (H )= U + pV(kJ) Or
Page 5
Properties of pure substances
Properties of Pure Substance
• A pure substance is a material with homogeneous and invariable
composition.
• Pure substances can have multiple phases, an ice water mixture is still a pure
substance but an air-steam is not a pure substance.
Pure Substance:
• A substance that has a fixed chemical composition throughout is called a
pure substance i.e., water, nitrogen, helium, and CO2.
• Substances which are mixture of various elements or compounds also
qualifies as pure substances as long as mixture is homogeneous.
Vapour Vapour
Liquid Liquid
(a) H2 0 (b) Air
Saturation Temperature and Saturation Pressure:
• At given pressure, the temperature at which a pure substance changes phase
is called the saturation temperature Tsat.
• Likewise at a given temperature, the pressure at which a pure substance
changes phase is called the saturation pressure psat.
Example: For water at a pressure of 101.325 kPa, Tsat is 100°C, conversely at a
temperature of 100°C, psat is 101.325 kPa.
Latent Heat:
• The amount of energy absorbed or released during a phase change process is
called the latent heat.
• The amount of energy absorbed during melting is called the latent heat of
vaporization.
• Similarly, the amount of energy absorbed during vaporization is called latent
heat of vaporization and is equivalent to the energy released during
condensation.
Liquid-Vapour Saturation Curve:
From the following figure, it is clear that Tsat increases with psat. Thus, a substance
at higher pressure will boil at higher temperatures.
Tsat = f(Psat)
^sat •
• In the kitchen, higher boiling temperature means shorter cooking time and
energy saving.
• The atmospheric pressure, and thus the boiling temperature of water,
decreases with elevation. Therefore, it takes longer time to cook at higher
altitudes than it does at sea level.
Property Diagrams for Phase-change Process
The T-V Diagram:
• Consider piston cylinder device containing liquid water at 20°C and 1 atm.
• Water will start boiling at a much higher temperature (179.9°C) at inside
pressure of the cylinder reaches at 1 MP.
• The specific volume of the saturated liquid is larger and the specific volume of
the saturated vapour is smaller than the corresponding values at 1 atm
pressure. That is, the horizontal line that connects the saturated liquid and
saturated vapour states is much shorter.
• As the pressure is increased further, this saturation line will continue to get
shorter as shown in figure and it will become a point when the pressure
reaches 22.09 MPa for the case of water. This point is called the critical point
and it is defined as the point at which the saturated liquid and saturated
vapour state are identical.
• At pressure above the critical pressure, there will not be a distinct phase
change. Instead, the specific volume of the substance will continually
increase and at all times there will be only one phase present. It is customary
to refer to the substance as superheated vapour at temperature above the
critical temperature and as compressed liquid at temperatures below the
critical temperature.
T V diagram of constant pressure phase-change process of a
pure substances at various pressures.
The p-V Diagram:
• The general shape of the p-V diagram of a pure substance is very much like
the T-V diagram but the T = constant lines on this diagram have a downward
trend.
• Consider again a piston cylinder device that contains liquid water at 1 MPa
and 150°C, water at this state exists as a compressed liquid. Now, the weights
on top of the piston are removed one by one so that the pressure inside the
cylinder decreases gradually.
• The water is allowed to exchange heat with the surroundings so its
temperature remains constant.
• As the pressure decreases, the volume of the water will increase slightly,
when the pressure reaches the saturation pressure volume at the specific
temperature, the water will start to boil.
• During this vaporisation process, both the temperature and the pressure
remain constant but the specific volume increases. Once the last drop of
liquid is vaporised further reduction in pressure results in a further increase in
specific volume.
• If the process is repeated for other temperatures similar paths will be
obtained for the phase change processes.
Triple Phase:
• When all three phases of a pure substance co-exist in equilibrium. It is called
triple phase.
• Triple phase states form a line called the triple line.
• The triple line appears as a point on the p-T diagram and therefore is often
called the triple point.
p V diagram of pure substance
• No substance can exist in the liquid phase in stable equilibrium at pressure
below the triple point pressure.
• The same can be said for temperature for substance that contract on
freezing.
• Substances at high pressure can exist in the liquid phase at temperatures
below the triple point temperature.
The p-T Diagram:
• Solid - Liquid = Fusion
• Liquid - Vapour = Vaporisation
• Solid - Vapour = Sublimation
Substances that Substances that
expand on contract on
Enthalpy
• Enthalpy is a measure of the total energy of a thermodynamic system.
• It includes energy required to create a system and the amount of energy
required to make room for it by displacing its environment and establishing its
volume and pressure.
• For certain type of processes particularly in power generation and
refrigeration.
o Enthalpy (H )= U + pV(kJ) Or
per unit mass h = u + pV(kJ/kg)
Saturated Liquid and Saturated Vapour States:
• Subscript f-» properties of saturated liquid
• Subscript g -? properties of saturated vapour
• Vf _ specific volume of saturated liquid
• Vg _ specific volume of saturated vapour
• Vfg _ difference between Vg and Vfnthai
• Vfg =Vg-Vf
• hfg -? enthalpy of vaporisation or latent heat of vaporisation (amount of
energy need to vaporise a unit mass of saturated liquid at a given
temperature of pressure).
• The magnitude of latent heat depends on temperature and pressure at which
phase change occurs.
• For example at 1 atm pressure, the latent heat of fusion of water is 333.7
kj/kg and latent heat of vaporization is 2257.1 kj/kg.
• At below triple point pressure, substance begins to change directly gas.
• Enthalpy of vaporization decreases as the temperature or pressure increases
and become zero at the critical point.
Saturated Liquid Vapour Mixture:
• During vaporisation process, a substance exists as part liquid and part
vapour.
• A new property quality x is the ratio of mass of vapour to the total mass of the
mixture.
Quality or dryness fraction:
x = — - —
m total = m liquid + m vapour = m f + m g
where, mf = mass of the saturated liquid, and mg = mass of the saturated vapour •
• Quality has significance for saturated mixtures only.
• It has no meaning in the compressed liquid or superheated region.
• Its value lie between 0 (saturated liquid) and 1 (saturated vapour).
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