Basic Thermodynamic Concepts

H, W, E

Chapter 1

Outline
1. What is Thermodynamics
Applications and Various Scales

2. Energy, Heat, and Work

Types of Energy and Work

3. Thermodynamic Systems
Isolated, Close, and Open Systems

4. Basic Thermodynamic Properties

Intensive and Extensive Properties

5. State and State Functions

State and Path Functions

6. Equilibrium

Thermodynamics is the only physical theory

of general nature of which I am convinced
that it will never be overthrown.
Albert Einstein

Nothing in life is certain except death, taxes,

and the laws of thermodynamics.
Seth Lloyd

1. Thermodynamics
Initially, study the effects of heat, work, and energy
Determine the state (PVT) at a given condition.
Estimate thermophysical properties (CP, H, H, )
Define equilibria and driving forces for physical
processes/chemical reactions

Cannot Do
Transition/transfer rates of physical processes
(heating/cooling, expansion/compression,
melting/freezing, vaporization/condensation, )
Reaction rates of chemical processes
(combustion, ammonia synthesis, hydrocarbon
cracking and conversion, )

N 2 + 3H 2 2NH 3

n-C6 2-methyl-C5 2,3-dimethyl-C4

Applications
Thermodynamics is one of the scientific cornerstones in science & engineering.

Process Design

Thermodynamics

Gas Separation

nano-thermodynamics

bio-thermodynamics

Drug Design

At Various Scales
Classical scale
(macroscopic)

Molecular scale
(mesoscopic)

H2, 1 mol
6.022 x 1023 H2 molecules

no molecular
information

a batch of
molecules

Electronic scale
(microscopic)
electronic structure
of one molecule
www.fzu.cz/~kolorenc/qmc/

2. Energy, Heat, and Work

Energy (E)

E, H, W

Heat (H)

Work (W)

Energy (E)
Energy = the ability to do work
Forms of Energy
Potential
Kinetic (translational, rotational, vibrational)
Internal (what is this?)

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Potential Energy (EP)

Potential energy is defined as the energy resulting
solely from the position in an external field. The
filed may be gravitational, electric or magnetic.
The gravitational potential energy is given by:

EP = mgh
m is mass
g is acceleration of gravity
h is height

reference

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Kinetic Energy (EK)

Kinetic energy is the energy of motion.
Translational motion:
EK = m v2 / 2
m is mass, v is translational velocity.

Rotational motion:
EK = I 2 / 2
I is inertia moment, is angular velocity.

Vibrational motion:
EK = k0 (r r0)2 / 2
k0 is force constant, r is position, r0 is equilibrium position.

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Internal Energy (U)

Energy of substance associated with the motions,
interactions and chemical bonding of molecules.
The translational, rotational and vibrational kinetic
energy of molecules.

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Heat (Q)
Heat is a form of energy transferred solely as a
result of temperature difference.

Zeroth law of thermodynamics:

Objects in thermal equilibrium
have the same temperature.

Heat added to system is defined as positive.

Heat released by system is defined as negative.

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Work (W)
Work is the transfer of energy.
Work done on system is defined as positive.
Work done by system is defined as negative.

Types of work:

Electrical
Shaft
Elastic
Mechanical
PV (Pressure-Volume)

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Electrical Work

Electrical work is expressed as kilowatt hour (kWh).

1 kWh = 3.6 million Joules
Watt: W = J/s = Nm /s = kgm2/s3

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Shaft Work
work from a stirrer

work from a crank

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Elastic Work
This type of work refers to the deformation of an
elastic object such as spring and flexible metal.
Hookes law relates stress to strain
(of force to deflection)

F(r ) = K r
r is the displacement of the end of the spring from its equilibrium position.

Elastic work for a displacement from r1 to r2 is:

W=
K (r r ) / 2
F dr =
(Kr ) dr =
2
2

2
1

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Mechanical Work
Basic definition of mechanical work:
work = force displacement

dW = F dh
Integrating
h2

W = F(h) dh

h1

By convention, the mechanical work is positive when the

displacement is in the same direction of the force and
negative when they are in opposite directions.

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PV Work
For piston-cylinder process, under Pext

V
dW =
F dh =
Pext A d =
Pext dV
A
Why ? By definition.

Pext

Pext

Psys

For a reversible process (Pext = Psys = P):

(e.g. very slow change along a continuous PV path)

Integrate dW = P dV
then

W = PdV

path dependent

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Reversible Process
Assumption:
Frictionless piston-cylinder
Balanced driving force
Very slow
Process:
Infinitesimal mass is removed from (or
added to) the piston in succession
Only Infinitesimal displacement of piston
with equilibrium maintained
Infinite time required for a finite change

How to know a reversible process? Look for keyword!

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Example: heat or mass transfer

T1

T2
T1 > T2

Finite difference in T,
the heat transfer is
irreversible

T1

T2

T1

T2
T1 = T2

T1 = T+dT T2 = T
Infinitesimal difference
in T, the heat transfer
is reversible

T1=T2, the heat

transfer is reversible
(in equilibrium)

permeable membrane

P1

P2

P1

P2

P1 > P2

P1 = P+dP P2 = P

Finite difference in P,
the mass transfer is
irreversible

Infinitesimal difference
in P, the mass transfer
is reversible

P1

P2

P1 = P2
P1 = P2, the mass
transfer is reversible
(in equilibrium)

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3. Thermodynamic Systems

System

Boundary

Surroundings

System: The portion (stationary or moving)

chosen for thermodynamic analysis
Surroundings: The portion outside the system

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Systems
Three types of systems

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Example:
Determine open, close or isolated system:

hot casting
300 C

(a)

(b)

(c)

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4. Basic Thermodynamic Properties

Properties of a system chosen for
thermodynamic analysis

T, P, V, U, H,
Cp, Cv .

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Intensive Properties
Independent of the amount of material

T
P
Specific properties (property per unit mass/mole)
Vm, specific volume (m3/kg, m3/kmol)
Um, specific internal energy (kJ/kg, kJ/kmol)
Hm, specific enthalpy (kJ/kg, kJ/kmol)
Cp, heat capacity at constant pressure (kJ/kg/K, kJ/kmol/K)
Cv, heat capacity at constant volume (kJ/kg/K, kJ/kmol/K)

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Extensive Properties
Directly proportional to the amount of material

Vt = mVm, total volume (m3)

Ut = mUm, total internal energy (kJ)
Ht = mHm, total enthalpy (kJ)

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Measurable & Conceptual Properties

Measurable thermodynamic properties
(T, P, V, , Cp, Cv)
Changes in conceptual properties can be
determined from measurable properties

U= Q + W

U =

T2

T1

dT

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5. State & State Functions

Thermodynamic state is the
total condition of a given system
as reflected by its thermodynamic
properties.
State functions: thermodynamic
properties whose values do not
depend on the path or past history.
Path functions: thermodynamic
properties whose values depend on
the path or past history.

1 mol H2O at
400 K & 1 bar

T, P, V, U,

2
b

a
1

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State Function

Path Function

T, P, V, U, H, S, etc.

Q, W

Independent of path or past history

Dependent of path or past history

Represented by point graphically

Represented by area graphically

No change in property for a cyclic

process

Change in property for a cyclic

process

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State functions which describe a system:

energy
volume
# of particles
entropy
pressure
chemical potential

E
V
N
S
P

electric potential
dipole momentum
viscosity
refractive index

How many state functions are necessary to describe a

unique system? The phase rule answers this question.

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6. Equilibrium
A macroscopic state, at which the state properties do not
change and have no tendency to change.
An equilibrium state is static in the macroscopic scale but
dynamic in the microscopic scale.

Thermodynamic state properties

measurable only at equilibrium.

are

defined

and

We can approximate equilibrium when state properties

change very slowly.

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Thermal equilibrium: equality of temperature.

(zeroth law of thermodynamics)
Mechanical equilibrium: equality of pressure.
Phase equilibrium: equality of chemical potential.
Chemical equilibrium: equality of chemical potential.
H2O(V)
100C, 1 bar
H2O(L)
100C, 1 bar
Vapor-Liquid phase equilibrium

Chemical reaction equilibrium

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Phase Rule (Gibbs)

F 2N

(for system at equilibrium only)

F: degree of freedom
: number of phases
N: number of chemical species
F = number of thermodynamic properties
defined system is well defined, all other
intensive thermodynamic properties are
defined and can be determined.

longitude & latitude

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Example:
(a) Pure liquid H2O F = 2-1+1 = 2.
If specify T, P (298 K, 1 bar) F = 0.

H2O(L) @
298 K, 1 bar

(b) Saturated vapor H2O in equilibrium with liquid H2O

F = 2-2+1 = 1. If specify T (100 C) F = 0.

H2O(V)
100C, 1 bar
H2O(L)
100C, 1 bar

Josiah Willard Gibbs

(1839-1903) American mathematical physicist
who contributed much of the theoretical
foundation for chemical thermodynamics.
Between 1876 and 1878, Gibbs wrote a series of papers
collectively titled On the Equilibrium of Heterogeneous
Substances.
Engineering began at Yale in 1852 with a course on civil
engineering. Yale awarded the first engineering Ph.D. in the
U.S. The recipient was J. Willard Gibbs (1858 B.S., 1863
Ph.D.) who would become one of this country's greatest
scientists. He was one of the earliest theoretical physicists in
U.S. and perhaps one of the earliest theoretical chemists. The
U.S. Postal Service honored Gibbs with a stamp in 2005.

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Summary
1. What is Thermodynamics
Applications, Various Scales

2. Energy, Heat, and Work

Types of Energy and Work

3. Thermodynamic Systems
Isolated, Close, and Open Systems

4. Basic Thermodynamic Properties

Intensive and Extensive Properties

5. State and State Functions

State and Path Functions

6. Equilibrium