1.

Pure substance

• Pure substance: A pure substance has a homogenous and fixed chemical

composition throughout, and may exist in more than one phase
• Air is a mixture of several gases, but it is considered to be a pure
substance.

PHYSICAL CHEMISTRY 1

Ngo Thanh An

1. Pure substance
1. Pure substance
• Saturated vapor: A vapor that is about to condense.
• Saturated liquid–vapor mixture: The state at which the liquid and vapor
• Compressed liquid (subcooled liquid): A substance that it is not phases coexist in equilibrium.
about to vaporize. • Superheated vapor: A vapor that is not about to condense (i.e., not a saturated
• Saturated liquid: A liquid that is about to vaporize. vapor).

At 1 atm and 20°C, water

exists in the liquid phase
(compressed liquid).

At 1 atm pressure and

100°C, water exists as
a liquid that is ready to As more heat is transferred, part of At 1 atm, the temp. remains As more heat is transferred,
vaporize (saturated the saturated liquid vaporizes constant at 100°C until the last the temperature of the
liquid). (saturated liquid–vapor mixture). drop of liquid is vaporized vapor starts to rise
(saturated vapor). (superheated vapor).
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1. Pure substance 1. Pure substance

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.
• The temperature at which water starts boiling depends on the pressure;
therefore, if the pressure is fixed, so is the boiling temperature.
• Water boils at 100°C at 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.

T-v diagram for the heating

process of water at The liquid–vapor saturation
constant pressure. curve of a pure substance
(numerical values are for
water).

5 6

1. Pure substance
1. Pure substance
• Latent heat: The amount of energy absorbed
or released during a phase-change process.
The variations of properties during phase-change processes are best studied and
• Latent heat of fusion: The amount of energy
understood with the help of property diagrams such as the T-v, P-v, and P-T diagrams
absorbed during melting. It is equivalent to
for pure substances.
the amount of energy released during
freezing.
• Latent heat of vaporization: The amount of
energy absorbed during vaporization and it is
equivalent to the energy released during
condensation.
T-v diagram of constant-pressure
• The magnitudes of the latent heats depend
phase-change processes of a pure
on the temperature or pressure at which the
phase change occurs. substance at various pressures
(numerical values are for water).
• 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.

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1. Pure substance 1. Pure substance
• saturated liquid line
• saturated vapor line
• compressed liquid region
• superheated vapor region
• saturated liquid–vapor mixture
region (wet region)

At supercritical pressures Critical point: The point at

(P > Pcr), there is no which the saturated liquid
distinct phase-change and saturated vapor states
(boiling) process. are identical.

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1. Pure substance 1. Pure substance

• For most substances, the relationships among thermodynamic properties are too
complex to be expressed by simple equations.
• Therefore, properties are frequently presented in the form of tables.
• Some thermodynamic properties can be measured easily, but others cannot and are
calculated by using the relations between them and measurable properties.
• The results of these measurements and calculations are presented in tables in a
convenient format.
Enthalpy—A Combination Property
Enthalpy of vaporization, hfg (Latent heat of
vaporization): The amount of energy needed
The combination u +
to vaporize a unit mass of saturated liquid at
Pv is frequently a given temperature or pressure.
encountered in the
analysis of control
volumes.
The product pressure ´ volume
has energy units.
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1. Pure substance 1. Pure substance

Quality, x : The ratio of the mass of vapor to the total mass of the mixture. Quality is
between 0 and 1 0: sat. liquid, 1: sat. vapor.
Examples: The properties of the saturated liquid are the same whether it exists alone or in a mixture
Saturated liquid and with saturated vapor.
saturated vapor states Temperature and pressure are
of water on T-v and P- dependent properties for a mixture.
v diagrams.

The relative
amounts of
liquid and
vapor phases
in a saturated
mixture are
specified by A two-phase system can be treated
the quality x. as a homogeneous mixture for
convenience.
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1. Pure substance 1. Pure substance

Examples: Saturated liquid-vapor mixture
states on T-v and P-v diagrams.

y v, u, or h.

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1. Pure substance 1. Pure substance
Compared to saturated vapor, superheated
In the region to the right of the
vapor is characterized by The compressed liquid properties depend Compressed liquid is characterized by
saturated vapor line and at on temperature much more strongly than
temperatures above the critical they do on pressure.
point temperature, a substance
y v, u, or h
exists as superheated vapor.
In this region, temperature and A more accurate relation for h
pressure are independent
properties.

At a specified P,
superheated
vapor exists at a
higher h than the
saturated vapor.

A compressed liquid may be

approximated as a saturated liquid at the
17 given temperature. 18

1. Pure substance 1. Pure substance

Example 1. Example 3 .
A rigid tank contains 50 kg of saturated An 80-L vessel contains 4 kg of refrigerant-134a at pressure of 160 kPa.
liquid water at 90ºC. Determine the Determine:
pressure in the tank and the volume of the (a) The temperature of the refrigerant
tank. (b) The quality
(P = 70.14 kPa, V = 0.0518 m3) (c) The enthalpy of the refrigerant
(d) The volume occupied by the vapor phase.
Example 2. (T=-15.60ºC, x = 0.157, h = 64.2 kJ/kg, vg = 0.0775 m3)

A mass of 200 g of saturated liquid water is

completely vaporized at a constant pressure
of 100 kPa. Determine the volume change
and amount of energy added to the water
Table A-5, at P=100 kPa,
vg=1.6950 m3/kg & vf=0.001043 m3/kg, hfg = 2258.0 kJ/kg

(ΔV =0.3387 m3, mhfg = 451.6 kJ)

1. Pure substance 2. Thermodynamic cycles

Example 4 .
Determine the temperature of water at a state of P = 0.5 MPa and h = Classification of thermodynamic cycle:
2890 kJ/kg.
(at P = 0.5 MPa, hg = 2748.7 kJ/kg
(T=216.3ºC)
• Power / refrigeration cycle
• Gas / vapor cycle
• Closed / open cycle

2. Thermodynamic cycles 2. Thermodynamic cycles

Otto cycle
Internal
combustion
engine Diesel cycle Carnot cycle
Gas turbine Gas cycle
Brayton cycle Stirling cycle
Jet engine

Power cycle
Rankine
Vapor cycle
cycle
Rankine
Steam turbine
cycle
External
combustion Stirling
engine cycle

Ericsson
cycle
2. Thermodynamic cycles 2. Thermodynamic cycles

Brayton cycle Ideal Diesel cycle Ideal Otto cycle

3. Carnot cycle 3. Carnot cycle

Diagrams for a Carnot Cycle

• Thermodynamic cycle for heat engines

• Describes the thermodynamic energy conversion process for
the most efficient heat engine.
• The cycle has 4 states.
• Q1 is the heat (i.e., energy) provided to the Carnot engine
• Q2 is the heat that the engine returns to the environment (heat
rejection)
• W is the work (i.e., energy) produced in one cycle

1–2 isothermal expansion (in contact with TH)

2–3 isentropic expansion to TC
3–4 isothermal compression (in contact with TC)
4–1 isentropic compression to TH
3. Carnot cycle 3. Carnot cycle

W = Q 1 - Q2
The Carnot engine is useful as an idealized
Q model.
Since dS = then Q = ò TdS
T All of the heat input originates from a source
S2 S4 at a single temperature, and all the rejected
W = Q1 - Q2 = ò T1dS - ò T2dS heat goes into a cold reservoir at a single
S1 S3
temperature.
W = Q1 - Q2 = (T1 - T2 )(S2 - S1 ) Since the efficiency can only depend on the
reservoir temperatures, the ratio of heats can
W (T1 - T2 )( S 2 - S1 ) T only depend on those temperatures.
Efficiency: h= h= = 1- 2
Q1 T1 (S 2 - S1 ) T1

• Observation #1: The efficiency increases as T1 increases (higher quality heat) and QC T
T2 (typically the ambient temperature) decreases. eCarnot = 1 - =1- C
• Observation #2: Since T2 can never be zero, the efficiency can never be 1. QH TH
• Observation #3: Stirling engines operation approximates a Carnot Cycle.

4. Power cycles (gas) 4. Power cycles (gas)

4. Power cycles (gas) 4. Power cycles (gas)

4. Power cycles (gas) 5. Power cycles (vapor)

• Vapor power cycle: the one in which the working fluid is

alternatively vaporized and condensed.
• Steam is the most common working fluid used in vapor
power cycles because of its many desirable
characteristics, such as low cost, availability, and high
enthalpy of vaporization.
5. Power cycles (vapor) 5. Power cycles (vapor)
Carnot cycle is the most efficient cycle operating between two specified
temperature limits. However, the Carnot cycle is not a suitable model for
power cycles.
Several impracticalities are associated with this cycle: Ideal cycle for vapor power cycles, consists of the following
· Temperature can not be higher than the critical temp. (374oC). four processes:
· Process 2-3: quality of steam is low à corrosion for turbine blade.
• 1-2 Isentropic compression in a pump
· Process 4-1: compress a two phase fluid is impossible
• 2-3 Constant pressure heat addition in a boiler
• 3-4 Isentropic expansion in a turbine
• 4-1 Constant pressure heat rejection in a condenser

5. Power cycles (vapor) 5. Power cycles (vapor)

Pump (q = 0) w pump,in = h2 - h1
w pump,in = v ´ (P2 - P1 )
h1 = h f @ P1 and v @ v1 = v f @ P1

Boiler (w = 0): qin = h3 - h2

Turbine (q = 0) wturb,out = h3 - h4

Condenser (w = 0): qout = h4 - h1

5. Power cycles (vapor) 5. Power cycles (vapor)

The thermal efficiency of the Rankine cycle is determined from

w net q
th = = 1 - out
qin qin

where : wnet = qin - qout = wturb,out - w pump,in

5. Power cycles (vapor) 5. Power cycles (vapor)

6. Refrigeration cycles 6. Refrigeration cycles

6. Refrigeration cycles 6. Refrigeration cycles

6. Refrigeration cycles 6. Refrigeration cycles

6. Refrigeration cycles 6. Refrigeration cycles