Вы находитесь на странице: 1из 41

Topics To Be Discuss

Introduction and Fundamentals of


Thermodynamics (Chapter 1)
The First Law of Thermodynamics for Close and
Open Systems (Chapter 2)
Equation of State (Chapter 3)
Heat Effects (Chapter 4)
The Second Law of Thermodynamics (Chapter 5)
Thermodynamic Properties of (Pure) Fluid
(Chapter 6)
Production of power from heat (Chapter 8)
Refrigeration & Liquefaction (Chapter 9)
Vapour-Liquid Equilibrium (Chapter 10)
Theory of Solution Thermodynamics (Chapter 11)
Chemical Reaction Equilibrium (Chapter 13)

Thermodynamics
Science of Energies.
Study of science of transfer &
Conversion of Energies from one
form to another and the study of
properties and characteristics of
matter needed for this transference.
Greek words: therme (heat) + dynamis
(power)
Thermodynamics Power developed
from heat

Types Of Thermodynamics
Classical thermodynamics formulate
the macroscopic state
Studies the average behavior of large
groups of Molecules
Defines macroscopic properties such as
temperature and pressure.
Statistical thermodynamics
formulate the microscopic state
Defines the properties of a system
based on the behavior of
molecules/atoms.

Chemical engineer &


thermodynamics
Calculation of heat and work requirements
for physical and chemical processes
Determination of equilibrium conditions for
Chemical reactions
Transfer of chemical species between
phases (mass transport)
Thermodynamics
deals with driving force
does not deal with RATEs of physical or
chemical phenomena
Rate=f(driving force, resistance)

Basic Thermodynamic
definitions
A system contains a substance with a large amount of
molecules or atoms, and is formed by a geometrical volume
of macroscopic dimensions subjected to controlled
experimental conditions
A simple system is a single state system with no internal
boundaries, and is not subject to external force fields or
inertial forces
A composite system has at least two simple systems
separated by a barrier restrictive to one form of energy or
matter
The boundary of the volume separates the system from its
surroundings
A system may be taken through a complete cycle of states, in
which its final state is the same as its original state

Closed and Open systems


Closed system:
Material content is fixed
Internal mass changes only due to a chemical reaction
Exchange energy only in the form of heat or work with the
surroundings

Open system:
Material and energy content are variable
Systems freely exchange mass and energy with their
surroundings

Other systems
Isolated system:
Cannot exchange energy and matter
Thermally insulated system:
System surrounded by an insulating
boundary
Universe:
A system and its surroundings

Processes
Energy conversion and degradation:
physical and chemical processes A process takes place in
a system!

Adiabatic process:
Any process within an adiabatic system (no heat transfer
through the system boundaries)

Steady state process: Input = Output


Variables in the system remain constant with time
System exchanges energy or matter at a constant rate

Unsteady state process (transient process):


Variables in the system change with time
Input = output + Accumulation

Infinitesimal process:
A process that takes place with only an infinitesimal change in
the macroscopic properties of a system

Thermodynamic properties
are derived from the statistical averaging of
the observable microscopic coordinates of
motion
If a thermodynamic property is a state
function
its change is independent of the path
between the initial and final states
depends on only the properties of the initial
and final states of the system
The infinitesimal change of a state function
is an exact differential

What do we mean by the State


of a System?
The state of a system is fixed by knowing a minimum
number of the system properties
EXTENSIVE
are additive and depend upon the mass of the system,
e.g. m, n, V, H, U, etc.
All extensive properties are homogeneous functions of
the first order in the mass of the system
Ex: Doubling the mass of a system at constant
composition doubles the internal energy
INTENSIVE
are not additive and do not depend upon the mass of the
system,e.g. P, T, refractive index, density, thermal
conductivity, etc.
Intensive properties can be expressed as derivatives of
extensive properties

Energy
Mechanical work of expansion or compression
proceeds with the observable motion of the coordinates of
the particles of matter
Chemical work proceeds with changes in internal
energy due to changes in the chemical composition (mass
action)
Potential energy is the capacity for mechanical
work
related to the position of a body
Kinetic energy is the capacity for mechanical work
related to the motion of a body
Potential and kinetic energies are external energies
Sensible heat and latent heat are internal energies

State Of Equilibrium
We only Apply Thermodynamics at
equilibrium
Mechanical
Mechanical Equilibrium
Equilibrium
no unbalanced forces
Chemical Equilibrium
no chemical potential differences
Thermal Equilibrium
no temperature differences
Phase Equilibrium
No phase change

Zeroth Law
Object A is in equilibrium with both
the thermometer and object B. Then
the thermometer should also be in
equilibrium with object B.
This means all three objects have the
same temperature

Temperature scales

Ideal Gas Thermometer

Substance gas
Property limit(pV)
Reference point
Interpolation

f (t)
Limit (pV)
p
0

Slope R
f(t) = Pv at triple point of water T = 22711.8
273.15 K
273.15K

Absolute Zero

Triple point of water

-273.15 C
f (t)= pV=0

0C

100 C

t (C)

Work: P-V

Internal Energy U
No concise thermodynamic definition
Cannot be directly measured
Only absolute values are known
(no reference point)
In thermodynamics, only changes in
internal energy are used
U=U2-U1

First law of
thermodynamics:
Conservation of energy

During a process:
Energy can be transferred and
converted from one form to another,
while the total energy remains
constant
(Energy of the system) + (Energy
of the surroundings) = 0
Finite change in quantity

First law of thermodynamics

Example 2.4 (Ref: Smith,Van


Ness, Abbott, 7th ed, p28)
When a system is taken from state a to
state b in Fig. 2.1 along path acb, 100 J
of heat flows into the system and the
system does 40 J of work.
a) How much heat flows into the system
along path aeb if the work done by the
system is 20 J?
b) The system returns from b to a along
path bda. If the work done on the
system is 30 J, does the system absorb
or liberate heat? How much?

James Prescott Joules


experiment

Problem 2.5 (Ref:


Smith,Van Ness, Abbott,
7th
ed,
p56)

One mole of gas in a closed system


undergoes a four-step
thermodynamic cycle. Use the data
given in the following table to
determine numerical values for the
missing quantities.

Constant-V and
Constant-P Process
Energy balance for n moles of a
homogeneous fluid contained in a
closed system:
d(nU) = dQ + dW
Mechanically reversible, closed
system:
dW = -Pd(nV)
Then d(nU) = dQ - Pd(nV)

@ Constant-V
If V = cnst dV = 0
for closed system dn = 0 dW = -Pd(nV) =
0
Then

Closed, constant volume system:


Heat transferred = Change in internal
energy

@ Constant-P

reversible, closed, constant pressure


system:
Heat transferred = Change in enthalpy

Enthalpy
Is used to calculate cooling and
heating processes (heat exchangers,
evaporators, distillation columns,
pumps, turbines, engines, etc)
appears in energy balances to
calculate Q and W

Ex: Enthalpy of moist and humid air sensible heat + latent


heat

Example 2.8(Ref: Smith,Van


Ness, Abbott, 7th ed, p39)
Calculate U and H for 1 kg of
water when it is vaporized at 100 C
and 101.33 kPa. Specific volumes of
liquid and vapor water at these
conditions are 0.00104 and 1.673
m3/kg. 2256.9 kJ of heat is added to
water for it to vaporize.

Solution:
System: 1 kg water @ constant T
Assumption: Mechanically reversible, closed,
constant P system
H = Q = 2256.9 kJ
H = U + (PV)
U = H PV
PV = 101.33 kPa * (1.673-0.00104) m3
=169.4 kJ
U = 2256.9 - 169.4 = 2087.5 kJ

Heat capacity @ constant V

Heat capacity @ constant P

General Energy Balance

Control volume with one


entrance-exit

MEASURE
OF DEVIATION FROM IDEAL-GAS
The farther away Z is from unity, the more the
Compressibility factor Z
BEHAVIOR
gas deviates from ideal-gas behavior.
A factor that accounts for
the deviation of real gases
from ideal-gas behavior at
a given temperature and
pressure.

Gases behave as an ideal gas at low densities


(i.e., low pressure, high temperature).
Question: What is the criteria for low pressure
and high temperature?
Answer: The pressure or temperature of a gas
is high or low relative to its critical temperature
or pressure.

Corresponding State Two Parameter


Reduced
pressure

Reduced
temperature
Pseudo-reduced
specific volume

Comparison of Z factors for various gases.

Z can also be determined from


a knowledge of PR and vR.

35

Principle of Corresponding
States

Lennard-Jones (LJ) 12/6 pairpotential


Interaction forces that exist between
molecules of any substance, typically at
very short intermolecular separation
distances (~ 5 20A(where 1A= 10-8m)

B/ r 12

A/r 6

Molecules for which the centres of positive


and negative charge coincide (for example,
methane) do not possess a permanent
dipole and are termed non-polar. When two
polar molecules approach each other
closely the electric fields of the dipoles
overlap, resulting in their re-orientation in
space such that there is a net attractive
force between them.

If the centre of total positive and negative


charges in a molecule do not coincide (for
example, for water), it results in a
permanent dipole, which imparts a polarity
to the molecule.
When molecules approach to distances
even less than ~ 5 A or so, a repulsive
interaction force comes into play due to
overlap of the electron clouds of each
molecule, which results in a repulsive force
field between them.

Virial EOS
Generally applicable to moderate
deviations from ideal gas behavior,
the virial EOS is given by two
alternate forms:

Pitzer Correlation

Acentric Factor
The compressibility factor for all fluids with
the same value of , when compared at the
same reduced temperature and pressure are
approximately the same, and hence the
deviation from ideal-gas behavior is nearly
the same.
Generalized Compressibility factor
Approach to EOS: Pitzer Correlations

OTHER EQUATIONS OF
STATE

Several equations have been proposed to


represent the P-v-T behavior of substances
accurately over a larger region with no
limitations.

Van der Waals


Equation of State

Critical isotherm
of a pure
substance has
an inflection
point at the
critical state.

This model includes two effects not considered


in the ideal-gas model: the intermolecular
attraction forces and the volume occupied by the
molecules themselves. The accuracy of the van
der Waals equation of state is often inadequate.

41

Вам также может понравиться