CEN 202 THERMODYNAMICS

CHAPTER 5: THE SECOND LAW OF THERMODYNAMICS

TEXT BOOK: : J. M. SMITH, H. C. VAN NESS, M. M. ABBOTT, M. T. SWIHART. “INTRODUCTION TO CHEMICAL ENGINEERING
THERMODYNAMICS”, EIGHTH EDITION. 2018
ENTROPY
Entropy is an intrinsic property for systems at internal equilibrium. Differential
changes in this property are given by the equation:

𝒕
𝒅𝑸𝒓𝒆𝒗
𝒅𝑺 =
𝑻
(1)
St : is the system (rather than the molar) entropy

THE SECOND LAW OF THERMODYNAMICS

The entropy change of any system and its surroundings, considered together, and
resulting from any real process, is positive, approaching zero when the process
approaches reversibility. Mathematically,
∆𝑺𝒕𝒐𝒕𝒂𝒍 ≥ 𝟎
(2)
The second law confirms that every process proceeds in such a direction that the
total entropy change associated with it is positive, the limiting value of zero
being attained only by a reversible process. No process is possible for which the
total entropy decreases.
The second law relates to:
 heat flows from hot to cold,
 limits to the conversion of heat to work by any device.
Application of the Second Law to Simple Heat Transfer
The equation for the entropy change of a heat reservoir follows from Eq. (1).
Because T is constant, integration gives:
𝑸
∆𝑺 =
𝑻
Q (heat) is transferred to or from a reservoir at temperature T

QH and QC have opposite signs:

Therefore, QH = − QC, and the entropy changes of the reservoirs at TH and at TC are:
𝑸 −𝑸 𝑸
∆𝑺𝒕𝑯 = 𝑯 = 𝑪 and ∆𝑺𝒕𝑪 = 𝑪
𝑻𝑯 𝑻𝑯 𝑻𝑪

Text Book: : J. M. Smith, H. C. Van Ness, M. M. Abbott, M. T. Swihart. “INTRODUCTION TO CHEMICAL ENGINEERING
THERMODYNAMICS”, EIGHTH EDITION. 2018
From these two entropy changes:

−𝑸𝑪 𝑸𝑪 𝑻𝑯 − 𝑻𝑪
∆𝑺𝒕𝒐𝒕𝒂𝒍 = ∆𝑺𝒕𝑯 + ∆𝑺𝒕𝑪 = + = 𝑸𝑪
𝑻𝑯 𝑻𝑪 𝑻𝑯 𝑻𝑪

Because the heat-transfer process is irreversible, Eq. (2) requires a positive value for ΔStotal, and therefore

QC (TH −TC) > 0

With the temperature difference positive, QC must also be positive, which means that heat flows into the reservoir at
TC, i.e., from the higher to the lower temperature.

As result:
No process is possible which consists solely of the transfer of heat from one temperature level to a higher one.

Text Book: : J. M. Smith, H. C. Van Ness, M. M. Abbott, M. T. Swihart. “INTRODUCTION TO CHEMICAL ENGINEERING
THERMODYNAMICS”, EIGHTH EDITION. 2018
Application of the Second Law to Heat Engines
Heat can be converted into work: heat engines
With respect to the engine, from the first law as given by Eq. ∆𝑈 = 𝑄 + 𝑊 becomes:

∆𝑼 = 𝑸 + 𝑾 = 𝑸𝑯 + 𝑸𝑪 + 𝑾

Because the engine inevitably operates in cycles, its properties over a cycle do not change.
Therefore, ΔU = 0, and W = −QH − QC.
The entropy change of the surroundings equals the sum of the entropy changes of the reservoirs. Because the
entropy change of the engine over a cycle is zero, the total entropy change is that of the heat reservoirs. Therefore
𝑸𝑯 𝑸𝑪
∆𝑺𝒕𝒐𝒕𝒂𝒍 =− −
𝑻𝑯 𝑻𝑪
Combining this equation with the equation for W to eliminate QH yields:
𝑻𝑯 − 𝑻𝑪
𝑾 = 𝑻𝑯 ∆𝑺𝒕𝒐𝒕𝒂𝒍 + 𝑸𝑪
𝑻𝑪

𝑻𝑯 −𝑻𝑪
If the engine is totally ineffective, W = 0;  ∆𝑺𝒕𝒐𝒕𝒂𝒍 = −𝑸𝑪
𝑻𝑯 𝑻𝑪

Text Book: : J. M. Smith, H. C. Van Ness, M. M. Abbott, M. T. Swihart. “INTRODUCTION TO CHEMICAL ENGINEERING
THERMODYNAMICS”, EIGHTH EDITION. 2018
Application of the Second Law to Heat Engines
If the process is reversible in all respects, then ΔStotal = 0, and the equation reduces to:
𝑻𝑯
𝑾 = 𝑸𝑪 −𝟏
𝑻𝑪

A heat engine operating as described in a completely reversible manner is very special and is called a Carnot
engine (an ideal engine), described by N. L. S. Carnot in 1824.
“It is impossible to construct an engine that, operating in a cycle, produces no effect (in system and
surroundings) other than the extraction of heat from a reservoir and the performance of an equivalent amount
of work”.
Combining this equation with W = −QH − QC to eliminate first W and then QC leads to Carnot’s equations:
𝑸𝑪 𝑸𝑯
− =
𝑻𝑪 𝑻𝑯

𝑾 𝑻𝑪 𝑻𝑪
= − 𝟏 → 𝑾 = 𝑸𝑯 −𝟏
𝑸𝑯 𝑻𝑯 𝑻𝑯
𝑻𝑪
the thermal efficiency of a Carnot engine: 𝜼𝑪𝒂𝒓𝒏𝒐𝒕 = 𝟏 −
𝑻𝑯

Text Book: : J. M. Smith, H. C. Van Ness, M. M. Abbott, M. T. Swihart. “INTRODUCTION TO CHEMICAL ENGINEERING
THERMODYNAMICS”, EIGHTH EDITION. 2018
HEAT PUMPS

HEAT PUMP
Because a Carnot engine is reversible, it may be operated in reverse; the Carnot cycle is then traversed in the

opposite direction, and it becomes a reversible HEAT PUMP operating between the same temperature levels
and with the same quantities QH, QC, and W as for the engine but reversed in direction (see the figure).

Text Book: : J. M. Smith, H. C. Van Ness, M. M. Abbott, M. T. Swihart. “INTRODUCTION TO CHEMICAL ENGINEERING
THERMODYNAMICS”, EIGHTH EDITION. 2018
ENTROPY CHANGES FOR THE IDEAL-GAS STATE
For one mole or a unit mass of fluid undergoing a mechanically reversible process in a closed system,
the first law:
𝒅𝑼 = 𝒅𝑸𝒓𝒆𝒗 − 𝑷𝒅𝑽
For the ideal-gas state, dHig = CPig dT and Vig = RT/P. As results of substitutions and division by T,
𝒅𝑸𝒓𝒆𝒗 𝒊𝒈 𝒅𝑻 𝒅𝑷
= 𝑪𝑷 −𝑹
𝑻 𝑻 𝑷
𝒊𝒈
𝒊𝒈 𝒅𝑻 𝒅𝑷 𝒅𝑺𝒊𝒈 𝑪𝑷 𝒅𝑻
𝒅𝑺𝒊𝒈 = 𝑪𝑷 𝑻 − 𝑹𝑷 or = − 𝒅𝒍𝒏𝑷
𝑹 𝑹 𝑻

where Sig is the molar entropy for the ideal-gas state. Integration from an initial state at conditions
T0 and P0 to a final state at conditions T and P gives:
𝑻 𝒊𝒈
∆𝑺𝒊𝒈 𝑪 𝒅𝑻 𝑷
=න 𝑷 − 𝒍𝒏
𝑹 𝑻𝟎 𝑹 𝑻 𝑷𝟎

Text Book: : J. M. Smith, H. C. Van Ness, M. M. Abbott, M. T. Swihart. “INTRODUCTION TO CHEMICAL ENGINEERING
THERMODYNAMICS”, EIGHTH EDITION. 2018