Chapter 1 - Basic Concepts of Thermodynamics

HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY – VNU HCM
CHAPTER 1
BASIC CONCEPTS OF THERMODYNAMICS

IDEAL GAS EQUATION OF STATE
1. Basic definitions
2. State and property
3. Ideal gas equation of state + mixture of ideal gases
1
Lecturer: Dr. Phan Thanh Nhan
BASIC CONCEPTS OF THERMODYNAMICS
2
1. Basic definitions
THERMODYNAMICS is the science that deals with heat & work and those properties of
substances that bear a relation to heat & work
Energy conversion:
Thermodynamics? Heat work
Historically, thermodynamics developed out of need

to increase the efficiency of early steam engines
Applications:
 air conditioning, heat pump, refrigeration system…
 vapor power cycles
 pump, fan, compressor
 drying equipment
 engines: steam turbine, gas turbine, internal engine, …
 gas separation, liquefaction …
 wind energy, solar energy, geometry energy, tidal energy… 3
Dimension and Units: International System
Dimension Unit
Area m2
Volume m3
Velocity m/s
Acceleration m/s2
Density kg/m3
Pressure Pascal (Pa)
Force Newton (N)
Work, Energy Joule (J)
Power Watt (W)
4
Thermodynamic system or system

Thermodynamic system = a device or combination of devices
containing a quantity of matter that is being studied
Surroundings = everything outside of the system
boundary = surface separated between the quantity of matter inside and
surrounding
What is “quantity of matter”?

exams: heat engine: air
steam engine: steam
internal engine: fuel + air
refrigeration system: refrigerants (Freon, NH3…)
5
A control volume contains the matter and devices inside a control surface
(below left)—also known as an OPEN SYSTEM
A control mass contains the same amount of matter at all times (below
right)—also known as a CLOSED SYSTEM
An isolated system has no mass or energy transfer across its boundary
(example?)
6
Thermal energy reservoirs (heat reservoirs) ?

Thermal energy source + thermal energy sink ?
Thermal equipment?
Heat engine,
Heat pump and refrigerator
 Heat engine: A system that operates in a
cycle and performs a net positive work and a
net positive heat transfer. The substance to
which and from heat is transferred is the
working fluid.
7
Heat engine
Heat transferred from high temperature reservoir (at TH) = QH
Heat transferred to low temperature reservoir (at TL) = QL
Define thermal efficiency ηthermal:
Wnet QH  QL QL
 thermal    1
QH QH QH
Note that 0 ≤ ηthermal < 1; typical values ~ 0.25 for automobile engines,
0.35 for coal-fired power plants, 0.60 for combined cycle gas turbine
plants where the waste heat from the gas turbine is used to make steam to
generate additional electricity via a steam turbine; this last step enhances
the efficiency
8
 Refrigerator or Heat Pump: A device

that operates in a cycle that requires work
and accomplishes the objective of
transferring heat from a low-temperature
body to a high temperature body
9
Heat transferred to the surroundings (at TH) = QH

Heat transferred from low temperature space (at TL) = QL
Refrigerator
Define coefficient of performance :
Q L (energy sought) QL 1
  
Wnet (energy th at costs) Q H  Q L Q H /Q L  1
Heat pump
For a heat pump, the objective is to supply heat to a warm space from
cold surroundings; in this case, the energy sought is QH and the
coefficient of performance  is
Q H (energy sought) QH 1
  
Wnet (energy th at costs) Q H  Q L 1  Q L /Q H
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2. State and property
A phase is a quantity of matter that is uniform throughout
A state is described by certain observable macroscopic properties (T, P, density…)
Each of the properties of a substance in a given state has only one definite value
and ALWAYS has the same value for a given state
Intensive properties are independent of the quantity of matter that is present
(examples?)
Extensive properties depend on the quantity of matter that is present (examples?)
Equilibrium is achieved when the value of a property is uniform throughout a
system (examples?)
Thermodynamic equilibrium is equilibrium regarding all possible changes of
state
11
Processes and Cycles

When does a change of state occur?
Whenever one more of the properties of a system change
In moving from an initial state to a final state, the system undergoes
a succession of states that make up a process
Example: piston-cylinder
If we remove all the weights at once, the piston rises
quickly and is not in equilibrium at any point
between its initial and final states. If we remove a
very small amount of weight at a time, the system
goes through a series of “quasi-equilibrium” steps in
which an infinitessimal change in properties occurs
between each step. This is called an IDEAL
PROCESS
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Processes and Cycles

For non-equilibrium processes, we can only describe the initial and
final states of a system and none of the states in between.
A system undergoes a cycle when it passes through a series of states
and returns to its original state.
Several processes are described by one constant property, i.e.
Constant temperature process = ??
Constant pressure process = ??
Constant volume process = ??
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Properties
Properties use to defined the state of system and the state of system is
completely specified by two independent properties
+ Temperature
+ Pressure
+ Density, specific volume
+ Internal energy
+ Enthalpy
+ Entropy
14
Temperature Scales
• Until 1954, the Celcius scale was based on two fixed, easily
duplicated points (the ice point and steam point) at 1 atm
pressure
• In 1954, the scale was redefined in terms of the triple point
of water as 0.01 oC and the ideal gas temperature scale
• The absolute or thermodynamic temperature (Kelvin) scale
is independent of any substance
TK   tC  273,15

Celcius t _ oC
Kelvin T _ K tF  TR  459,67
Fahrenheit _ oF F  32
tC 
1,8
Rankine _ oR
T(R )  1,8.T(K) 15
Pressure
Pressure is defined as the force exerted by a fluid per unit area
Fn
P  lim
AA ' A
1 Pa = 1 N/m2
1 bar = 105 Pa = 0.1 MPa
1 atm = 101325 Pa = 101.325 kPa
Gauge pressure = Pabs – Patm
In thermodynamics we are primarily
concerned with absolute pressure,
relative to a vacuum
16
Pressure Measurements
Consider the column of fluid of height H
above point B in the manometer shown :
P0 A  mg  P0 A  AgH
where m  mass of fluid column, A  cross - sectional
area,   density
This force must be balanced by the upward force at
the bottom of the column, which is PB A.
PB  P0  gH
Since points A and B are at the same elevation, their
pressures must be equal. The pressure in the vessel P
is equal to PA and the fluid in the vessel has a much
lower density t han that in the column. Overall,
P  P  P0  gH
17
Specific Volume and Density

Specific Volume = v = volume per unit mass (m3/kg)
v is an intensive property
Total volume = V (m3)
V is an extensive property
Density = ρ = mass per unit volume (kg/m3 or g/cm3)
ρ is an intensive property
V 3 1 G
v (m / kg)    (kg / m3 )
G v V
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The Zeroth Law of Thermodynamics
BLOCK A BLOCK B BLOCK C
Assume that block B is brought into contact with block A until they
achieve the same temperature according to a thermometer.
Block B is now brought into contact with block C and the thermometer
indicates thermal equilibrium.
The Zeroth Law of Thermodynamics states that when two bodies have
equality of temperature with a third body, they in turn have equality of
temperature with each other.
19
Internal energy U
Internal energy is the sum of microscopic energy (related to the molecular
structure of a system and the degree of the molecular activity)
=> Internal energy depend on temperature and specific volume U = f(T, v)
Mass: G(kg)
Internal energy: U(kJ)
Internal energy on a unit mass basic: u (J/kg)
Unit:
kJ, kcal, kWh,
Btu (Bristish thermal unit),
Chu (Centigrade heat unit)
1 kcal = 4,18kJ = 4,18kW.s = 1/861,24 kWh

1Btu = 1,055kJ = 0,55555Chu
20
Enthalpy I
21
Entropy S
- In 1865, Clausius realized a new thermodynamic property and he chose

to name this property Entropy
Q
dS 
T
- to find the entropy difference between any two states of a system, the
integral must be evaluated for some reversible path between the initial
and final states. Since entropy is a state function
- the entropy change of the system for an irreversible path is the same
as for a reversible path between the same two states.
Unit: kJ/kg.K or kcal/kg.K
22
3. Ideal gas equation of state + mixture of ideal gases

Ideal gas?
 An ideal gas is a theoretical gas composed of many randomly moving
point particles whose only interactions are perfectly elastic collisions
 a hypothetical gas whose molecules occupy negligible space ( v = 0) and
have no interactions( f = 0), and which consequently obeys the gas laws
exactly.
Ideal gas equation of state?
pV = GRT pv = RT
white:
p : absolute pressure, N/m2.
V : volume, m3. R8314
G : mass, kg. R  (J / kg.K)
T : absolute temperature, K.
 
R : gas constant, J/kgK.
23
Example:
24
Mixture of ideal gases

Many thermodynamic applications involve mixtures of ideal gases.
Mixture of ideal gases:
+ each of the gases in the mixture individually behaves as an ideal gas
+ the gases in the mixture do not react with one another to any
significant degree.
Air is an example of an ideal gas mixture and has the following

approximate composition.
Component % by Volume
N2 78.10
O2 20.95
Argon 0.92
CO2 + trace elements 0.03
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 partial pressure:
Consider placing each of the k gases in a separate container having the volume
of the mixture at the temperature of the mixture. The pressure that results is
called the component pressure, Pi'
26
Gibbs-Dalton’s law:
The total pressure exerted by a mixture of gages which do not interact chemically
is equal to the sum of partial pressure, where the partial pressure of gas is the
pressure exerted by this individual gas at the same temperature of the mixture if it
alone occupies the same volume of the mixture
n
p   pi pi: component pressure
i 1 p: pressure of mixture
n
U   Ui
Ui: component internal energy
i 1 U: internal energy of mixture
27
 partial volume
The partial volume vA in the mixture is defined as the volume that would be
occupied nA moles of A alone only for ideal gases at the total pressure p at
the same temperature T of the mixture
28
Amagat’s law:
Amagat's law of additive volumes states that the volume of a gas mixture
is equal to the sum of the volumes each gas would occupy if it existed
alone at the mixture temperature and pressure.
n
V   Vi
i 1
Vi: component volume

V: volume of mixture
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The properties of the mixture may be based on the mass of each component,
called gravimetric analysis, or on the moles of each component, called molar analysis.
Mass fraction
Gi
gi 
G n
  gi  1
n
G   Gi
i 1
i 1
Volume fraction:
Vi
ri 
V n
  ri  1
n
V   Vi
i 1
i 1
Mole fraction Vi n i
ri  
V n
30
To change from a mole fraction analysis to a mass fraction analysis, we can show that
G i i .n i
gi  
G .n
i
 gi  ri

To change from a mass fraction analysis to a mole fraction analysis, we can show that
ni n
ri   n i
 ni
n
i 1
g i i
 ri  n
g
i 1
i i
31
 determine some parameters of mixture
the average molar mass for the mixture 

Base on mole fraction
n n
i n
g 1  ri  1    ri . i
i 1 
i
i 1 i 1
Base on mass fraction
G G G 1 1
  n
 n  n
 n
Gi
M 
M gi

Gi 1
i 1
i
i 1  i
 .
i 1 G  i i 1  i
Molar mass for the mixture: 

Component molar mass: i 32
Gas constant R of mixture

From ideal gas equation (with pi, Ti = T, Vi = V)
pi V
p i V = G i Ri T or GiRi = T
Expressed:
n n
pi V pV

i 1
GiR i  
i 1 T

T
 GR
n n
GiR i
R   gi R i
i 1 G i 1
The apparent (or average) gas constant of a mixture is expressed as
8314
R (J/kg.K)

33
Partial pressure of component

piV = GiRiT and pV = GRT
pi V G i R i T GR
  pi  p i i
pV GRT GR
Ri
pi  pgi
R
R = .R= iRi = 8314 J/kmol.độ
Ri 
 
R i

p i  pgi pi = ri.p
i
The partial pressure of component i is defined as the product of the mole fraction and
the mixture pressure according to Dalton’s law 34
Summary for ideal gases mixture
Depend on mass fraction Depend on mole fraction

(or volume fraction)
Gas constant R of
mixture
Rm (J/kg.K)
Specific volume of
mixture v (m3/kg)
Partial pressure of
component pi
35
Example:
An ideal gas mixture at 2 atm and 35oC has the following volume composition
O2 15%
N2 65%
CO2 12%
CO 7%
H20 1%
a) Determine the partial pressures of each species
b) What are the mass fraction of oxygen and carbon monoxide in the mixture
c) What is the average molecular weight of the gas mixture
d) What is the density of the gas mixture
36
Example:
37
Example:
38
Be healthy and stay safe

See you on the next chapter!
39

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HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY – VNU HCM

BASIC CONCEPTS OF THERMODYNAMICS

2. State and property

3. Ideal gas equation of state + mixture of ideal gases

BASIC CONCEPTS OF THERMODYNAMICS

Thermodynamics? Heat work

Historically, thermodynamics developed out of need

Dimension and Units: International System

Thermodynamic system or system

What is “quantity of matter”?

Thermal energy reservoirs (heat reservoirs) ?

 Refrigerator or Heat Pump: A device

Heat transferred to the surroundings (at TH) = QH

Processes and Cycles

Processes and Cycles

TK   tC  273,15

Kelvin T _ K tF  TR  459,67

Specific Volume and Density

The Zeroth Law of Thermodynamics

BLOCK A BLOCK B BLOCK C

1 kcal = 4,18kJ = 4,18kW.s = 1/861,24 kWh

- In 1865, Clausius realized a new thermodynamic property and he chose

Unit: kJ/kg.K or kcal/kg.K

3. Ideal gas equation of state + mixture of ideal gases

Ideal gas equation of state?

Mixture of ideal gases

Air is an example of an ideal gas mixture and has the following

i 1 U: internal energy of mixture

Vi: component volume

 determine some parameters of mixture

the average molar mass for the mixture 

Base on mass fraction

Molar mass for the mixture: 

Gas constant R of mixture

The apparent (or average) gas constant of a mixture is expressed as

Partial pressure of component

R = .R= iRi = 8314 J/kmol.độ

Summary for ideal gases mixture

Depend on mass fraction Depend on mole fraction

Be healthy and stay safe

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