Chapter 3 - Contents

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CHAPTER 3: 2nd LAW OF THERMODYNAMIC

Chapter 3 - Contents
3.1 Entropy & entropy calculation
3.2 Reversible & irreversible process
3.1 Entropy, S

S describes the dispersal of energy and matter. The greater the dispersal of
energy or matter, the higher its entropy. The greater dispersal, the more
disorder the system becomes. Adding heat to a material increases the disorder.

S = 0.0 J/molK for a


pure crystalline at 0K.

At what temperature ∆S is the highest?

http://chem-faculty.lsu.edu/stanley/webpub/1422-Chapt-15-Thermodynamics.pdf
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3.2 Entropy & entropy calculation

dqrev
For closed, reversible process, the change in entropy, dS
T
a. Cyclic process, S = 0

b. Reversible adiabatic, dqrev = 0. Thus, S = 0

c. Reversible, phase change at constant T and P


2
dqrev 1 2 qrev H
S dqrev
1 T T 1 T T

d. Reversible, isothermal process


S = qrev/T

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3.2 Entropy & entropy calculation (continue ..)

Problem Example:
Heat evaporation for water at 100°C is 40.66 kJ/mol. Calculate
S when 5.00g steam condenses to liquid at 100°C and 1 atm.

Solution:
2
dqrev 12 qrev
S dqrev
1 T T 1 T
( 40.66 kJ/mol)(1mol/18g)(5. 00g)
30.27 J/K
(100 273.15)K

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3.2 Entropy & entropy calculation (continue ..)

e. Reversible, change of state for ideal gas


T2 T2
CV (T ) V2 CV (T ) P1T2
S dT nR ln dT nR ln
T1
T V1 T1
T P2T1

f. Irreversible state change for ideal gas S 0 since process


is irreversible. Calculation of S similar as in e.
Problem Example:
Calculate S when 24mg N2 at 89torr and 22oC
expands adiabatically into a vacuum at 34torr.

Solution: (= isothermal expansion)


T is constant, therefore,
P1T2 24mg 89
S nR ln 8.314J/mol.K ln 6.9mJ/K
P2T1 28g/mol 34
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3.2 Entropy & entropy calculation (continue ..)

g. Ideal gas, a, is mixed with ideal gas, b, at constant T


na
mix S na R ln xa nb R ln xb where, x a
n a nb

h. Heating at constant P w/o change of phase


T2
CP T2
S dT if CP is independent of T, S CP ln
T1
T T1

Problem Example:
Calculate S when 100g water is heated irreversibly from
50oC to 75oC at 1atm. CP remains constant at 1.00 cal/(goC).

Solution:
T2 T2 1.00kal 1J 348.15
S C P ln mcP ln 100g ln 31.18J/K
T1 T1 g K 0.23901kal 323.15

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3.3 Reversible & irreversible process

i. Reversible process – heat transfer between system & surrounding


prevails w/o visible temperature change. The system &
surrounding can be returned to their initial states.
Heat into system = (dqrev)syst
Heat into surrounding = - (dqrev)surr
Thus, dSuniv=dSsyst + dSsurr = 0
Suniv = 0

ii. Irreversible process – the system and surrounding cannot be


returned to their original state.
Ssyst 0, Suniv 0
Entropy increases to a maximum when the process attains
equilibrium.
(gas mixture, chemical rx., flow of heat into cold body, etc.)

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Summary of past lectures

1. Gas equation of state? Real vs ideal?


2. 1 law? ∆U=q+w, q=?, w=?
3. 2 law? dS=dq/T rev/irrev?

Next chapter - Solution

G=H-TS

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