Saint Louis University

School of Engineering and Architecture

Department of Chemical Engineering

THERMODYNAMICS 1

SUBMITTED BY:

Stefani Ann Cabalza

Jonalyn Tiru
Jediel Hermann Ocampo

SUBMITTED TO:

Engr. Jonalyn A. Kimpay

1 | Thermodynamics 1

History and important people

1600s Basic physical notions of heat and temperature were established

1700s it became widely believed that heat was instead a separate fluid-like substance

1840s Experiments by James Joule and others. He examined the heat produced by both
electrical and mechanical means, and was convinced that the various forms of energy
could be converted one into another. By measuring the heat produced in water by a
paddle wheel he deduced that 772 foot-pounds of mechanical work was equivalent to
the heat required to raise one pound of water by 1o F. In modern units this would make
1cal=4.15J, the current value being 1cal=4.184J.

1850s it became accepted that heat is in fact a form of energy

1824 Sadi Carnot had captured some of the ideas of thermodynamics in his discussion of the
efficiency of an idealized engine. Carnot deduced that the maximum amount of work that
could be extracted from an engine was when it was operating reversibly, and the
efficiency of such an engine, defined as the ratio of the work done (w), to the heat
supplied (qh), depended only on the two temperatures between which it operated.

1850 Rudolf Clausius and William Thomson (Kelvin) stated both the First Law - that total
energy is conserved - and the Second Law of Thermodynamics. The Second Law was
originally formulated in terms of the fact that heat does not spontaneously flow from a
colder body to a hotter. Other formulations followed quickly, and Kelvin in particular
understood some of the laws general implications.

1738 The idea that gases consist of molecules in motion had been discussed in some detail
by Daniel Bernoulli

1860 James Clerk Maxwell derived from the mechanics of individual molecular collisions the
expected distribution of molecular speeds in a gas

Clausius had introduced entropy as a ratio of heat to temperature, and had stated the
Second Law in terms of the increase of this quantity. Boltzmann then showed that his
equation implied the so-called H Theorem, which states that a quantity equal to entropy
in equilibrium must always increase with time. At first, it seemed that Boltzmann had
successfully proved the Second Law. But then it was noticed that since molecular
collisions were assumed reversible, his derivation could be run in reverse, and would
then imply the opposite of the Second Law. Much later it was realized that Boltzmanns
original equation implicitly assumed that molecules are uncorrelated before each
collision, but not afterwards, thereby introducing a fundamental asymmetry in time.

1872 Ludwig Boltzmann constructed an equation that he thought could describe the detailed
time development of a gas, whether in equilibrium or not. The form of this equation is
consistent with the fact that entropies are additive but probabilities (which determine W)
are multiplicative. Note also that as W cannot be less than one, S is always positive.

Early 1870s Maxwell and Kelvin appear to have already understood that the Second Law
could not formally be derived from microscopic physics, but must somehow be a
consequence of human inability to track large numbers of molecules.
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1876 In responding to objections concerning reversibility Boltzmann realized that in a gas

there are many more states that seem random than seem orderly. This realization
led him to argue that entropy must be proportional to the logarithm of the number of
possible states of a system, and to formulate ideas about ergodicity.

1900 Willard Gibbs introduced two state functions that are important in interpreting the
energies of systems at constant pressure and temperature. One of these H is now
called the enthalpy, and the other, G called the Gibbs energy (earlier the Gibbs free
energy). Gibbs showed that changes in H were given by the heat change in a
process, and that the minimum of the function G is the equilibrium condition for such
a system. G also measures the maximum work that can be extracted from a system
at constant pressure and temperature.

1930s Second Law had somehow come to be generally regarded as a principle of physics
whose foundations should be questioned only as a curiosity.

1940s it was recognized that entropy is simply the negative of the information quantity
introduced by Claude Shannon

TRIVIAS

REFERENCES

Introduction to chemical engineering thermodynamics by Hendrick C. Van Ness, J.M. Smith,

Michael M. Abbot, Mcgraw-Hill

Stephen Wolfram, A New Kind of Science. Notes for Chapter 9: Fundamental Physics. Section:
Irreversibility and the Second Law of Thermodynamics Page 1019
3 | Thermodynamics 1

FORMULAS FOR THERMODYNAMICS 1

MEASURES OF AMOUNT OF SIZE FIRST LAW OF THERMODYNAMICS

Specific volume = Esystem + Esurroundings = 0
Esurroundings = Q W
Molar volume, Vm =
Esystem = U + PE + KE
Q W = U + PE + KE
FORCE
1 For closed systems: (PE and KE are constant)
=
E = U = Q + W
For finite changes: U = Q + W
PRESSURE For differential changes: dU = dQ + dW

= =
Enthalpy:
H = U + PV
WORK For finite changes: H = U + (PV); H = U + VP +
= U PV
For differential changes: dH = dU + d(PV)
ENERGY For constant pressure process: H = U + PV
a. Kinetic energy
1 2 Heat Capacity:
= 2 =
2 2 Constant pressure: Q = H = nCpT
b. Potential energy Constant volume: Q = U = nCvT

= =
MATERIALS & ENERGY BALANCES FOR OPEN SYSTEMS
1u1A1 = 2u2A2 (continuity equation)

OVERALL ENERGY BALANCE EQUATION

2
W + Q = Z + 2 + H

EQUATIONS FOR PROCESS CALCULATIONS: IDEAL GAS

(Mechanically Reversible Closed-System Processes)
Q U H W
Isochoric U nCvT nCpT 0
Isobaric nCvT nCpT U - Q

Isothermal -W 0 0 RT 1 = RT 2
2 1
Adiabatic 0 nCvT nCpT U
4 | Thermodynamics 1

EQUATIONS OF STATE
Virial Equations
1. Application of virial equations

= = 1 + where B 2nd virial coefficient (equation 1)

= =1+ truncated in two terms (equation 2)


=
=1+ + 2
truncated in three terms (equation 3)

2. Extended virial equation: Benedict/Webb/Rubin Equation

0 0 0 / 2 2
= + 2
+ 3
+ 6 + 3 2 (1 + 2 ) /

3. Cubic equations of state

a. Van der Waals Equation of state

= 2

272 2
Where = =
64 8

b. Vapor & vapor-like roots of the generic cubic equation of state

()
= + [ ]
( )( + )

For Z: = 1 +
(+)(+)

= =

c. Vapor & vapor-like roots of the generic cubic equation of state

+
= + ( + )( + ) [ ]

For Z:
1+
= + ( + )( + ) [ ]

d. Other equations: Soave/Redlich/Kwong SRK Equation and Peng Robinson PR
Equation

Equation of
Tr Zc
state
VDW 1 0 0 1/8 27/64 3/8
RK Tr1/2 1 0 0.08664 0.42748 1/8
SRK SRK 1 0 0.08664 0.42748 1/8
PR PR 1 + 2 1 2 0.07779 0.45724 0.3074
1/2 2
= [1 + (0.480 + 1.574 0.1762 ) (1 )]
1/2 2
= [1 + (0.37464 + 1.5422 0.269922 ) (1 )]
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