CHE127: PHYSICAL CHEMISTRY FOR ENGINEERING 2

COURSE CONTENT
1. Review of 2nd and 3rd law of Thermodynamics
2. Spontaneity, equilibrium, and Free Energies
3. Physical Equilibrium : Single Component
4. Physical Equilibrium : Multiple Component
Physical Equilibrium : L-V Equilibria
5. Physical Equilibrium : L-L Equilibria
6. Chemical Equilibria
7. Ionic Equilibria
8. Electrochemistry
9. Quantum Mechanics

GRADING SYSTEM : PASSING 50%

LECTURE : 65%
LAB : 35%

LECTURE:
MIDTERM: 20%
FINAL EXAM: 20%
LONG EXAM: 35%
QUIZ: 15%
100%

LAB:
PRE-LAB: 30%
LAB: 30%
P 40%
100%
 Review of the 2nd and 3rd Law of Thermodynamics
Outline
1. Definition of Spontaneity
2. Definition and statements of the 2nd Law of Thermodynamics
3. Carnot cycle
4. Entropy
5. Useful equations for Reversible Processes
6. Isothermal Mixing of Gases
7. Entropy during phase changes
8. Entropy During Chemical Changes
9. Definition and Statements of the 3rd Law of Thermodynamic
10. 3rd Law Entropy
11. Absolute entropies of liquids and Gases
12. Debye Extrapolation

I. SPONTANEITY
- The natural occurrence of processes
- A spontaneous direction of change does not require work to be done to bring it
about.
 The spontaneous flow of heat is always unidirectional from the
higher to the lower temperature
- All naturaaly occurring processes always tend to change spontaneously in a direction
which will lead to equilibrium.
- performing a non-spontaneous process can be possible, but only if a certain amount
of work is done

II. DEFINITION AND STATEMENTS OF THE 2ND LAW OF THERMODYNAMICS

o Recognizes between the spontaneous and non-spontaneous processes
o Places a limitation to the 1stlaw, which does not have any restrictions on the
source of the heat or direction of its flow

Statements:
1) Clausius Statement
- It is impossible for a self-acting machine unaided by an external agency to move
heat from one body to another at a higher temperature.
2) Kelvin-Planck Statement
- It is impossible to construct a heat engine which, while operating in a cycle,
produces no effects except to do work and exchange heat with a single
reservoir.

3) Kelvin statement
- No process is possible in which the sole result is the absorption of heat from a
reservoir and its complete conversion into work.
4) The Entropy of an isolated system never decreases.
∆ S≥0
- limiting condition
- Reversible process

III. CARNOT CYLE

Carnot Engine
- Heat engines that operate in a reversible manner.

Carnot’s Theorem:
For a 2 given heat reservoirs, no engine can have a thermal efficiency higher
than that of a Carnot engine.

Carnot Cycle
Cycle: a series of operations so conducted that at the end, the system is
back to its original state
- Named after the French Engineer Sadi Carnot
- Consist of 4 stages

4 STAGES OF CARNOT CYCLE

1. REVERSIBLE ISOTHERMAL EXPANSION
FROM A TO B AT TH

q w

PA PB
TA TB
VA TA = TB VB
VB > VA
UA = qA + WA
+
2. REVERIBLE ADIABATIC EXPANSION FROM B TO C UNTIL TEMPERATURE
DECREASES FROM TH TO TC

WB
PB PC
TB TC
VB dq = 0 VC
Vc > V b
UA = Wb
+
3. REVERSIBLE ISOTHERMAL COMPRESSION FROM C TO D AT TC
qc
Pc PD
Tc TD
Vc VD

Vd < Vc Wc
Uc = qc + Wc

4. REVERSIBLE ADIABATIC COMPRESSION FROM D TO A UNTIL TEMPERATURE

INCREASES FROM TC TO TH
WD
PD PA
TD TA
qd = 0
VD VA
Ud = Wd

∆ U =0
∆ U T =∆ U A +∆ U B +∆ U C + ∆ U D ¿ ∆ U A +∆ U B+ ∆ U C + ∆U D
= q A + W A – W b – q b + Wc + Wd
= (qa – qb ) – (WA – Wb) + Wc + Wd

THERMODYNAMIC EFFICIENCY
W NET
η= Carnot cycle
q1 q2 T c
W NET q1−q2 =
= q1 T H
q1 q1 - Lord Kelvin
q2
η=1−
q1
Tc
η=1−
TH
 CHECKPOINT #1
What is the efficiency of a reversible cyclic engine that operated between
reservoirs at 100C and 3000C?
A) 96.67%
B) 3.33%
C) 50.6%
D) 49.38%

IV.ENTROPY,S
- Measure of energy dispersed in a process
- A state function; a change in entropy occurs as a result of a physical or a
chemical change, this change is at the extent to which energy is dispersed in
a disorderly manner

The 2nd law statement in terms of entropy:

A spontaneous change is directed towards a more disorderly dispersal of
the total energy of the isolated system. ΔStotal > 0 where ΔStotal - total entropy of
the system and the surroundings.

The thermodynamic definition of entropy:

dQ rev
dS=
T
 f
dQ rev
∆ S=∫
i T
For surroundings,
dQ surr
dS surr =
T surr

dQ surr
∆ S=
T surr
For an adiabatic change,
∆ S sur =0

For Inequality,
∆ S≥0

Checkpoint # 2
In an isolated system at 300.0 K, an ideal gas expands reversibly. This requires 900.0
J of heat from the reservoir. Calculate the entropy changes (in J/K) of the gas, the
reservoir, and the entire system.
a) -3.0, 3.0, 0
b) 3.0, -3.0, 0
c) 0, 3.0, 3.0
d) 3.0, 0, 3.0
 V. USEFUL EQUATIONS FOR REVERSIBLE PROCESSES

T2 V2
∆ S=n C v ln +nRln
T1 V1

T2 P1
∆ S=n C p ln +nRln
T1 P2

V2 P2
∆ S=n C p ln +nRln
V1 P1

VI. ISOTHERMAL MIXING OF GASES

A B A B
PAO, NA PBO, NB PA, NA PBO, NB

∆ SA ∆ SB n A + nB = nT
PA = XAPT
PB = XBPT
PA P AO
∆ S A =−n A R ln =nRln
P AO PA

PB PB O
∆ S B=−nB Rln =nRln
PBO PB
PAO PB O
∆ S M =n A Rln =n+ Rln
X A PT X B P❑T

If PT = PAo = PBO :
1 1
∆ S M =n A Rln =n+ Rln
XA XB

VII. ENTROPY DURING PHASE CHANGES

- Phase changes under 1 atm pressure are reversible process
∆ H trans
∆ S=
T trans
TROUTON’S RULE
- Many normal liquids have approximately the same standard entropy of
vaporization which is 85 J/(K-mol).
 ∆ H trans J
∆ S= ∆ H TRANS =T trans∗85
T trans K−mol

VIII. ENTROPY CHANGES DURING CHEMICAL PROCESS

Entropy changes of chemical processes are usually evaluated at constant
temperature and pressure.

For the reaction: A + bB+…  cC+ dD+…

∆ S 0r =∑ ( n S0m ) products −∑ ( n S0m ) reactants

TEMPERATURE DEPENDENCE OF THE ENTROPY OF A REACTION:

For the reaction: A + bB+…  cC+ dD+…

T2
∆ C P dT
∆ S2 −S 1=∫ where Cp = a + bT + cT2
T1
T

When Cp is assumed constant over the T inrterval:

T2
dT
∆ S2 −S 1=∆ C P ∫
T1
T

IX. DEFINITION AND STATEMENTS OF THE 3RD LAW OF THERMODYNAMICS

1) It is impossible to attain the absolute zero of temperature.

2) NERNST HEAT THEOREM: In an isothermal process involving condensed pure

substances in equilibrium, the entropy change approaches zero as the absolute
temperature approaches zero and equals zero when the temperature equals
zero.

3) At absolute zero temperatures, the entropy of all pure perfect crystalline

structures may be taken to be zero.

X. 3RD LAW ENTROPY

Entropies reported on the basis that So = 0.
 Allows for the computation of the entropy of pure substances
S0 at 298 K = standard state entropy

XI. ABSOLUTE ENTROPIES OF LIQUIDS AND GASES

The total absolute entropy of a substance in a particular state at a given

temperature will be the sum of all the entropy changes that the substance has to
undergo in order to reach the particular state from the crystalline solid to absolute
zero.

q
NOTE: ∆ S=
T
S @ T = 200 C H2O  H2O
System: H2O @ T = 0 K @ T = 200 C

H2O H2O H2O H2O H 2O H 2O

T=0K 273 K 273 K 373.15 K 373.15 K 473.15 K
Solid solid liquid liquid vapor vapor

∆ ST =∆ S 1+ ∆ S 2+ ∆ S3 +∆ S 4 +∆ S5
S
C dt
∫ ∆ S=∫ TP (1,3,5 ) ∆ S
S
0
 XII. DEBYE EXTRAPOLATION
Heat capacities, Cp at low temperatures (T<=15K) follow the relationship:
CP = aT3
Debye heat capacity Rule
@T  15 K @T  16 K Use CP = aT3 CP ln T/T0

REMEMBER !!!
o q
o INTERNAL ENERGY, U
dU = Cvdt dU = dq + dW
dU = dq + dW dq = dU – dW
dV
d q=CvdT + RT
o ENTHALPY V
dH = CpDt dP
d q=CvdT + R d T −RT
dH = dV + d(PV) P
o WORK dH = dU + d(PV)
dW = -PdV dH = dq + dW + PdV + VdP
W = - PV dH = dq – PdV + PdV + VdP
RT dq = dH – VdP
P=
V dq = CpdT -VdP
RT dq = CpdT – RT/P dP
dW = dV dq = CpdT – RT dP/P
V
dV
dW =−RT RT
V dq=CpdT −Vd
RT V
V=
P
o dW =−Pd (
RT
)
dq=CpdT −RVd
T
V( )
V VdT −TdV
dq=CpdT −RV ( )
T V2
dW =−R Pd( ) 2
P R V d T RVTdV
dq=CpdT − 2
+ 2
V V
dV
dq=CpdT −RdT + RT
V
 Pd T −TdP
dW =−RP( 2
)
P
−R P 2 dT RT dP
dW = +
❑2 P2

dP
dW =−Rd T + RT ( )
❑
 SAMPLE PROBLEMS:
1) A sample consisting of 1.00 mol monoatomic perfect gas is heated from 100.00C to
300.00C at constant pressure. Calculate ΔS for the system.
2) A sample consisting of 3.00 mol diatomic gas at 200.0 K is compressed reversibly
and adiabatically until its temperature reaches 250 K. Given that Cvm= 27.5 J/(K-
mol), calculate W, Q, ΔU, ΔH, and ΔS.
3) A system undergoes a process in which the entropy change is 2.41 J/K. During
the process, 1.00 kJ of heat is added to the system at 500 K. Is the process
thermodynamically reversible? Why or why not?

4) A 40 kg steel casting (Cp = 0.5 kJ/(kg-K)) at a temperature of 4500C is quenched

in 150.0 kg of oil (Cp = 2.5 kJ/(kg-K)) at 250C. If there are no heat losses, what
is the isobaric change in entropy of a) the casting; b) the oil; and c) both
considered together?

5) Calculate the change in entropy of a 4.00 mol diatomic gas if it is heated from
300.0 to 550.0 K and the pressure increases from 1.5 to 3.5 atm.
6) If 2.5 mol of N2and 4.0 mol Ar, initially at the same pressure and temperature,
are allowed to mix by removing a partition keeping them apart, what is the
entropy change?

7) Determine the entropy change at standard state of the reaction of hydrogen gas
and chlorine gas to form hydrogen chloride.
1. What is the efficiency of an engine that operates between 273 K and 373 K?

2. Determine the molar entropy of vaporization of butane in J mol-1K-1. The molar

heat of vaporization (ΔH) of liquid butane is 22.9 kJ mol-1, and the boiling point is
289 K.
3. What is the entropy change associated with the isothermal reversible expansion of
1.00 mol of an ideal gas, at 298.15 K, from 5.00 L to 15.00 L?

4. A sample of neon gas is cooled from 325 K to 175 K. At the same time, the
pressure increases from 1.00 bar to 7.50 bar. What is the molar entropy
change for the neon gas?
5. A sample containing 1.00 mol of helium gas is mixed with 2.00 mol of neon gas.
Assuming both gases are behaving ideally, what is the entropy of mixing?