2nd Law of Thermodynamics

1st Law: conservation of energy 2nd Law: What kind of information do we get from the 2nd law? 2nd law provides means for: determining (quantitatively) the best theoretical performance of a thermodynamic cycles. evaluating the factors that prevent us from reaching the best theoretical performance level. determining (quantitatively) the lost work potential (or availability destruction) in a process. When do we get the best theoretical performance? When a process takes place REVERSIBLY.

REVERSIBLE PROCESS: A process is called reversible if the system and all parts of its surroundings can be restored to their respective states after the process has occurred (without leaving any trace both on the system and on the surroundings). Factors that make a process irreversible are called IRREVERSIBILITIES. Examples of these factors are: Friction Heat Transfer Mixing Chemical Reaction

How do we quantify the extend of the irreversibilities in a process? By making an ENTROPY BALANCE.

ENTROPY, S (kJ/K) is a property. It is defined with respect to a reversible process:

Q S = S2 S1 = (kJ/K) T 12 REV

If a process is reversible and adiabatic (Q = 0), then S2 S1 = 0, S2 = S1. Such a process is called constant entropy or ISENTROPIC PROCESS.
Microscopically, entropy is a quantitative measure of molecular disorder in a system. Macroscopically, entropy is a measure of energy that is no longer available to perform useful work with the current environment indicating the extend of irreversibilities in a process.

ENTROPY BALANCE:
Sin Sout + S gen = (S )sys (kJ/K)

or in rate form:
dS & & & & Sin Sout + S gen = (S )sys = (kW/K) dt sys

In a reversible process, Sgen = 0, i.e., entropy is not generated. In an irreversible process, Sgen > 0. AS IRREVERSIBILITIES The increase in entropy principle: > 0 ; Irreversible process
S gen (kJ / K ) & S gen ( kW / K )

ENTROPY GENERATION

= 0 ; Reversible process < 0 ; Violation of 2nd law (impossible process)

Entropy can be transferred with heat and mass. Work does not carry entropy. It is entropy free. If a system is exchanging heat with a thermal reservoir (say surroundings) which is at a constant temperature, To, the amount of (or rate of) entropy exchange will be
& Q Q . or To To
& The amount of (or rate of) entropy carried with a mass, m, or with a mass flow, m is & m s (kJ/K) or m s (kW/K) where s is the specific entropy (kJ/kg K) of the mass being carried.

Entropy Balance for Closed Systems:

Sin Sout + S gen = (S )sys (kJ/K) Qj S gen = (S2 S1 ) (kJ/K) Tj

j j

S gen = m( s2 s1 )

Qj Tj

(kJ/K)

Entropy Balance for Open Systems (Control Volumes):

dS & & & & Sin Sout + S gen = (S )sys = (kW/K) dt sys

& Qj + & Tj

& mi si

dS & & me se + S gen = dt sys

(kW/K)

Steady-Flow Systems:
& S gen =

& me se

& mi si

& Qj & Tj

(kW/K)

One inlet/one exit/one heat exchange with a reservoir at a temperature, To. & Qsys & & S gen = m (se si ) (kW/K) To Transient or Unsteady (Uniform) Flow Systems:
S gen =

me se

mi si

Qj Tj

+ (m2 s2 m1s1 ) (kJ/K)

One inlet/one exit/one heat exchange with a reservoir at a temperature To. Qsys S gen =m e se mi si + (m2 s2 m1s1 ) (kJ/K) To

How to find the entropy or the entropy change of a substance undergoing a process?
Use the tables (water and R-134a). Use the approximate relations obtained from Tds equations when you have an ideal gas.

Entropy Change of an Ideal Gas (Approximate relations) Assuming constant specific heats (from state 1 to state 2):
T s2 s1 = C ln 2 + R ln 2 kJ/kg.K T1 1 T P s2 s1 = C p ln 2 R ln 2 kJ/kg.K T1 P 1

VALID FOR A PROCESS OF AN IDEAL GAS SUCH AS AIR, CO2, N2ETC.

Isentropic Process of an Ideal Gas:

The process MUST be ISENTROPIC. Ideal gas relation MUST be valid. We assume constant specific heat values.

Then between states 1 and 2 (s2 = s1):

T2 P2 = T P 1 1
k 1 k T 2 1 ; T = 1 2 k 1

P2 1 ; P = 1 2

where k=cp/cv