Chemical Engineering

Thermodynamics
Unit 1
Fundamental Concepts and the
first Law of Thermodynamics
 Nomenclature

• • A area (m2) • • h convective heat transfer

• • CP specific heat at constant • coefficient (W/(m2×K)
• pressure (kJ/(kg×K)) • • K Kelvin degrees
• • CV specific heat at constant volume • • k specific heat ratio, CP/CV
• (kJ/(kg×K)) • • k 103
• • COP coefficient of performance • • kt thermal conductivity (W/(m-°C))
• • d exact differential • • M molecular weight or molar mass
• • E stored energy (kJ) • (kg/kmol)
• • e stored energy per unit mass • • M 106
• (kJ/kg) • • m mass (kg)
• • F force (N) • • N moles (kmol)
• • g acceleration of gravity • • n polytropic exponent (isentropic
• ( 9.807 m/s2) • process, ideal gas n = k)
• • H enthalpy (H= U + PV) (kJ) • • h isentropic efficiency for turbines,
• • h specific enthalpy (h= u + Pv) • compressors, nozzles
• (kJ/kg) • • hth thermal efficiency (net work
• done/heat added)
• • P pressure (kPa, MPa, psia, psig)
• • Pa Pascal (N/m2)
 Nomenclature cntd.
• X distance (m) • • R particular gas constant
• • X exergy (kJ) • (kJ/(kg×K))
• • x quality • • Ru universal gas constant
• • Z elevation (m) • (= 8.314 kJ/(kmol×K) )
• • Wnet net work done [(Wout - • • S entropy (kJ/K)
• Win)other + Wb] (kJ) where Wb = • • s specific entropy (kJ/(kg×K))
• for closed systems and 0 for • • T temperature ( °C, K, °F, R)
• control volumes • • U internal energy (kJ)
• • wnet Wnet /m, net work done per unit • • u specific internal energy
• mass (kJ/kg) • (kJ/(kg ×K))
• • Wt weight (N) • δ inexact differential • • V volume (m3 )
• • e regenerator effectiveness • ϕ relative • • volume flow rate (m3/s)
humidity • • velocity (m/s)
• • r density (kg/m3) • • v specific volume (m3/kg)
• • w humidity ratio • • molar specific volume (m3/kmol)
• • Qnet net heat transfer (Qin - Qout)
• (kJ)
• • qnet Qnet /m, net heat transfer per
• unit mass (kJ/kg)
 Subscripts, superscripts

• • A actual • P constant pressure

• • B boundary • • REF refrigerator
• • F saturated liquid state • • rev reversible
• • G saturated vapor state • • s isentropic or constant
• • fg saturated vapor value • entropy or reversible,
• minus saturated liquid • adiabatic
• value • • sat saturation value
• • gen generation • • v constant volume
• • H high temperature • • 1 initial state
• • HP heat pump • • 2 finial state
• • L low temperature • • i inlet state
• • net net heat added to system • • e exit state
• or net work done by system • • × per unit time
• • other work done by shaft and
• electrical means
 INTRODUCTION

• The study of thermodynamics is concerned with

the ways energy is stored within a
• body and how energy transformations, which
involve heat and work, may take place.
• One of the most fundamental laws of nature is
the conservation of energy principle. It
• simply states that during an energy interaction,
energy can change from one form to
• another but the total amount of energy remains
constant. That is, energy cannot be
• created or destroyed.
 Thermodynamics Intro
• Based on the macroscopic approach where a large number of particles,
called molecules, make up the substance in question.

• Macroscopic approach to thermodynamics does not require knowledge

of the behavior of individual particles and is called classical
thermodynamics.

• A direct and easy way to obtain the solution of engineering problems

without being overly cumbersome.

• Statistical thermodynamics - A more elaborate approach, based on the

average behavior of large groups of individual particles.

• Microscopic approach is rather involved and is not reviewed here and

leads to the definition of the second law of thermodynamics.

• The second law of thermodynamics approached from the classical point

of view and asserts that energy has quality as well as quantity, and
actual processes occur in the direction of decreasing quality of energy.
 Closed, Open, & Isolated
systems
• System: a quantity of matter or a region in
space chosen for study. is called the

• Surroundings: The region outside the system.

• Boundary : The real or imaginary surface that

separates the system from its surroundings. The
boundary of a system may be fixed or movable.
Surroundings : Physical space outside the system boundary.

Systems may be considered to be closed or open, depending on whether a

fixed mass or a fixed volume in space is chosen for study.
 Closed system
• A fixed amount of
mass and no mass
may cross the system
boundary.

• The closed system

boundary may move
as in the case of a
piston in a cylinder.
• Examples of closed systems
-sealed tanks and piston
cylinder devices (note the
volume does not have to
be fixed).

Energy in the form of heat and

work may cross the
boundaries of a closed
system
• Open system, or control
volume, has mass as well
as energy crossing the
boundary, called a control
surface.

• Examples of open
systems are pumps,
• compressors, turbines,
valves, and heat
exchangers.
 Isolated system: A general system of fixed mass
where no heat or work may cross the
boundaries. An isolated system is a closed
•system with no energy crossing the
boundaries and is normally a collection of a
main system and its surroundings
that are exchanging mass and energy
among themselves and no other system.
Properties
Density
Force
 Steady-Flow Process
• Fluid flowing through an open system or control volume such as a
water heater often defined by the terms steady and uniform.

• Steady flow: No changes with time.

• Uniform flow: No change with location over a specified region.

• Steady-flow devices: Engineering flow devices that operate for long

• periods of time under the same conditions

• The processes for these devices is called the steady-flow process.

• The fluid properties can change from point to point within the control
volume, but at any fixed point the properties remain the same during
the entire process.
 State Postulate
• The state of a system is described by its properties but
not all properties must be known before the state is
specified.

• Once a sufficient number of properties are known, the

state is specified and all other properties are known. The
number of properties required to fix the state of a simple,
homogeneous system is given by the state postulate:

– The thermodynamic state of a simple compressible system

is completely specified by two independent, intensive
properties.
 Cycle
• Cycle: A process (or a series of connected
processes) with identical end states

• Below is a cycle composed of processes,

A and B.
 ENERGY

Consider the system shown below moving

with a velocity, at an elevation Z relative to
the reference plane.
 ENERGY
• Total energy E of a system= sum of all forms of energy
that can exist within the system
– thermal, mechanical, kinetic, potential, electric, magnetic,
chemical, and nuclear.
– total energy of the system is normally thought of as the sum of the
internal energy, kinetic energy, and potential energy.

• The internal energy U is that energy associated with the

molecular structure of a system and the degree of the
molecular activity

• The kinetic energy KE exists as a result of the system's

motion relative to an external reference frame.
– When the system moves with velocity the kinetic energy is
expressed as

KE  1 mv 2 (kJ )
2
 Potential Energy
• PE-The energy that a system possesses
as a result of its elevation in a gravitational
field relative to the external reference
frame

• PE = mgZ (kJ)

• Total Energy: E=U+KE+PE (kJ)

 On a unit mass basis

where e = E/m is the specific stored energy,

u = U/m is the specific internal energy.

The change in stored energy of a system is given by

 Closed systens
• Most closed systems remain stationary
during a process thus, no change in their
kinetic and potential energies.

• The change in the stored energy is

identical to the change in internal energy
for stationary systems.
 Energy, Heat, Work & Sign convention
Energy may cross the boundary of a closed system only by heat or work.
– temperature difference between a system and its surroundings is called heat.

Energy transferred across a system boundary that can be thought of as the energy
expended to lift a weight is called work.

– Heat and work are energy transport mechanisms between a system and its
– surroundings.

• The similarities between heat and work are as follows:

– 1.Both are recognized at the boundaries of a system as they cross the boundaries. They
are both boundary phenomena.

– 2.Systems possess energy, but not heat or work.

– 3.Both are associated with a process, not a state. Unlike properties, heat or work has no
meaning at a state.

– 4.Both are path functions (i.e., their magnitudes depends on the path followed during a
process as well as the end states.
 Example
• If a large stone is dropped from a cliff 10.0 m
high how fast will it be going when it hits the
ground?
 END
•