Thermodynamics II

By
Peyman Moradi

Department of Chemical Engineering

Kermanshah University of Technology

The Reference:
“Introduction to Chemical Engineering Thermodynamics, 7th
Edition” by Smith, Van Ness & Abbott

Homework and Exams

Midterm: 25%
Final: 50%
Homework: 15%
participation in class discussions: 10%

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 Chapter 8

Production of Power
from Heat

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 Steam Power Plant

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 Carnot Engine cycle

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 Carnot Engine cycle

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 The Rankine cycle

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 Simple Practical Power cycle

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Example 8.1
Steam generated in a power plant at a pressure of 8,600 kPa and temperature of
500°C is fed to a turbine. Exhaust from the turbine enters a condenser at 10 kPa,
where it is condensed to saturated liquid, which is then pumped to the boiler. (a)
Determine the thermal efficiency of a Rankine cycle operating at these
conditions. (b) Determine the thermal efficiency of a practical cycle operating at
these conditions if the turbine efficiency and pump efficiency are both 0.75. (c) If
the rating of the power cycle of part (b) is 80,000 kW, what is the steam rate and
what are the heat-transfer rates in the boiler and condenser?

Solution :
(a) The turbine operates under the same conditions as the turbine of Example 7.6,
where we found

Moreover, we found the enthalpy at the end of isentropic expansion (H'2 in

Example 7.6) to be
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 Internal Combustion Engine
The Otto Engine
Work is produced. Adiabatic
expansion of the high T and P
The mixture is ignited and products of the combustion
combustion occurs so
rapidly that it is at constant
volume

The exhaust valves open

All valves are closed and the and P falls rapidly at
fuel/air mixture is nearly constant volume
compressed adiabatically

Piston moving outward

draws a fuel/air mixture Piston pushes the remaining of
into the cylinder combustion gases from the cylinder

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 Four Stroke Engine

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 Air- Standard Otto Cycle

Heat is absorbed by the

air at constant volume Reversible adiabatic expansion

Cooling at
Reversible adiabatic compression constant
volume

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 Air- Standard Otto Cycle- Thermal Eff.

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 The Diesel Engine

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 Diesel Engine
The diesel engine was first patented in 1892 by Rudolph Diesel.

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 Air- Standard Diesel- Thermal Eff.

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 Difference between petrol engine and Diesel engine

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 The Gas-Turbine Engine

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 Ideal Cycle for Gas-Turbine Engine
The Brayton Cycle
Working fluid is air taken as an ideal gas with constant heat capacities.

Addition of heat(the combustion)

An isentropic expansion
produces work
Reversible adiabatic
compression

a constant pressure cooling

completes the cycle

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 The Turbojet Engine

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 The Rocket Engine

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 Chapter 10
Vapor- Liquid Equilibrium:
Introduction

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1. THE NATURE OF EQUILIBRIUM
Equilibrium is a static condition in which no changes occur in the macroscopic properties
of a system with time. This implies a balance of all potentials that may cause change.

2. Measures of Composition
Mass or mole fraction:

Molar concentration is defined as the ratio of the mole fraction of a particular

chemical species in a mixture or solution to its molar volume:

The molar mass of a mixture or solution is, by definition, the mole-fraction-

weighted sum of the molar masses of all species present:

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3. VLE: QUALITATIVE BEHAVIOR
Vapor- Liquid equilibrium (VLE) is the state of coexistence of liquid and vapor phases. In
this qualitative discussion, we limit consideration to systems comprised of two chemical
species.

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 4. SIMPLE MODELS FOR VLE

Raoult’s Law

The two major assumptions required to reduce VLE calculations to

Raoult’s law are:

1. The vapor phase is an ideal gas.

2. The liquid phase is an ideal solution.

Raoult’s Law - restrictions

The first assumption means that Raoult’s law can apply only for low to moderate
pressures.

The second assumption implies that the law can have approximate validity only
when the system species are chemically similar.

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Raoult’s Law - mathematical expression

xi is a liquid phase mole fraction,

yi is a vapor phase mole fraction,
Pisat is the vapor pressure of pure species i at the temperature of the
system.
The product yi P is known as the partial pressure of species i.

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 Dewpoint and Bubblepoint Calculations with Raoult's Law

Dew point and Bubble point Calculations Equations used for the
calculations:

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Example 10.1

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 Henry’s law
For a species present as a very dilute solute in the liquid phase, the partial pressure of the
species in the vapor phase is directly proportional to its liquid-phase mole fraction:

Henry’s constants come from experiment, and Table 10.1 lists values at 25℃ for a few
gases dissolved in water.

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Example 10.2

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5. VLE modified Raoult’s law

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Example 10.3
For the system methanol (1)/methyl acetate (2), the following equations provide a reasonable
correlation for the activity coefficients:
ln  1  ( 2.771  0.00523T ) x22 ln  2  ( 2.771  0.00523T ) x12
The Antoine equations provide vapor pressures:
3643.31 2665.54
ln P1sat / kPa  16.59158  ln P2sat / kPa  14.25326 
T ( K )  33.424 T ( K )  53.424
Calculate
(a): P and {yi} for T = 318.15 K and x1 = 0.25
(b): P and {xi} for T = 318.15 K and y1 = 0.60
(c): T and {yi} for P = 101.33 kPa and x1 = 0.85
(d): T and {xi} for P = 101.33 kPa and y1 = 0.40
(e): the azeotropic pressure and the azeotropic composition for T = 318.15 K

(a) for T = 318.15, and x1 = 0.25

P1sat  44.51 P2sat  65.64  1  1.864  2  1.072

P   xi i Pi sat  (0.25)(1.864 )( 44.51)  (0.75)(1.072 )(65.64)  73.50

i

yi P  xi i Pi sat y1  0.282 y 2  0.718

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(b): for T = 318.15 K and y1 = 0.60
P1sat  44.51 P2sat  65.64
1
P
An iterative process is applied, with 1  1 2 1
 i ii
y / 
i
P sat

y1 P
x1  x2  1  x1
 1 P1sat
Converges at: P  62.89 kPa  1  1.0378  2  2.0935 x1  0.8169
(c): for P = 101.33 kPa and x1 = 0.85
T1sat  337.71 T2sat  330.08
A iterative process is applied, with T  (0.85)T1sat  (0.15)T2sat  336.57

 1  ...  2  ...
3643.31
ln P1sat / kPa  16.59158 
T ( K )  33.424 P   xi i Pi sat
i

P1sat  ...
Converges at: T  331 .20 K  1  1.0236  2  2.1182 y1  0.670 y 2  0.330
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(d): for P = 101.33 kPa and y1 = 0.40

T1sat  337.71 T2sat  330.08

A iterative process is applied, with T  (0.40)T1sat  (0.60)T2sat  333.13

1  1  2  1
Bi
ln Pi sat / kPa  Ai 
T ( K )  Ci

P1sat  ... P2sat  ...

3643.31
ln P1sat / kPa  16.59158  P   xi i Pi sat
T ( K )  33.424
i

x1  ... x2  ...

 1  ...  2  ...

P1sat  ... P2sat  ...

Converges at: T  326 .70 K  1  1.3629  2  1.2523 x1  0.4602 x2  0.5398

54

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 (e): the azeotropic pressure and the azeotropic composition for T = 318.15 K
y1
x1 yi P  xi i Pi sat  1 P1sat
Define the relative volatility: 12  12 
y2  2 P2sat
x2

Azeotrope y1  x1 y 2  x2 12  1

P1sat exp( 2.771  0.00523T ) P1sat

12 x1  0   2.052 12 x1 1   0.224
P2sat
P2 exp( 2.771  0.00523T )
sat

Since α12 is a continuous function of x1: from 2.052 to 0.224, α12 = 1 at some point
There exists the azeotrope!

 1 P1sat  1az P2sat

12  1  sat  1.4747
 2 P2sat
2 az
P1

ln  1  ( 2.771  0.00523T ) x22 1

ln  ( 2.771  0.00523T )( x2  x1 )  ( 2.771  0.00523T )(1  2 x1 )
ln  2  ( 2.771  0.00523T ) x12 2
 1az  1.657
x  0.325  y
az
1
az
1
P az   1az P1sat  73.76 kPa
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6. VLE FROM K-VALUE CORRELATIONS

A convenient measure, the K-value: K  yi

i
xi

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For light hydrocarbon systems (methane to decane), the K values have been
determined semi-emperically

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Example 10.4
For a mixture of 10 mol-% methane, 20 mol-% ethane, and 70 mol-% propane at 50°F,
determine: (a) the dewpoint pressure, (b) the bubblepoint pressure. The K-values are given by
Fig. 10.13.
(a) at its dewpoint, only an insignificant amount of liquid is present:

P = 100 (psia) P = 150 (psia) P = 126 (psia)

Species yi Ki yi /Ki Ki yi /Ki Ki yi /Ki
Methane 0.10 20.0 0.005 13.2 0.008 16.0 0.006
Ethane 0.20 3.25 0.062 2.25 0.089 2.65 0.075
Propane 0.70 0.92 0.761 0.65 1.077 0.762 0.919
Σ (yi /Ki) = 0.828 Σ (yi /Ki) = 1.174 Σ (yi /Ki) = 1.000
(b) at bubblepoint, the system is almost completely condensed:

P = 380 (psia) P = 400 (psia) P = 385 (psia)

Species xi Ki xi Ki Ki xi Ki Ki xi Ki
Methane 0.10 5.60 0.560 5.25 0.525 5.49 0.549
Ethane 0.20 1.11 0.222 1.07 0.214 1.10 0.220
Propane 0.70 0.335 0.235 0.32 0.224 0.33 0.231
Σ(xi Ki) = 1.017 Σ(xi Ki) = 0.963 Σ(xi Ki) = 1.000

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 Flash calculations
• A liquid at a pressure equal to or greater than its bubblepoint
pressure “flashes” or partially evaporates when the pressure
is reduced, producing a two-phase system of vapor and liquid
in equilibrium.
• Consider a system containing one mole of nonreacting
chemical species:

L V  1 zi  xi L  yiV zi  xi (1  V )  yiV

zi K i
The moles of vapor The vapor mole fraction yi 
1  V ( K i  1)
zi K i
 1  V ( K  1)  1
The moles of liquid The liquid mole fraction
i

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 Example 10.5
The system acetone (1)/acetonitrile (2)/nitromethane(3) at 80°C and 110 kPa has the overall
composition, z1 = 0.45, z2 = 0.35, z3 = 0.20, Assuming that Raoult’s law is appropriate to this
system, determine L, V, {xi}, and {yi}. The vapor pressures of the pure species are given.

Do a BUBL P calculation, with {zi} = {xi} :

Pbubl  x1 P1sat  x2 P2sat  x3 P3sat  (0.45)(195.75)  (0.35)(97.84)  (0.20)(50.32)  132.40 kPa
Do a DEW P calculation, with {zi} = {yi} :
1
Pdew   101.52 kPa
y1 / P1sat  y2 / P2  y3 / P3
sat sat
L  1  V  0.2636 mol
Since Pdew < P = 110 kPa < Pbubl, the system is in the two-phase region,

Pi sat zi K i
Ki  K1  1.7795 K 2  0.8895 K 3  0.4575  1  V ( K  1)  1 V  0.7364 mol
P i

zi K i
yi 
1  V ( K i  1)
yi
x1  0.2859 Ki  y1  0.5087
xi
x2  0.3810 y 2  0.3389
x3  0.3331 y3  0.1524 61
 Chapter 11

Solution Thermodynamics:
Theory

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 Fundamental Property Relations

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 GPHS
U VAT
Great Physicists Have Study
Under Very Able Teachers

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 THE CHEMICAL POTENTIAL AND PHASE EQUILIBRIA

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 PARTIAL PROPERTIES

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 Equations Relating Molar and
Partial Molar Properties

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 Partial Properties in Binary Solutions
Written for a binary solution, the summability relation, Eq. (1 1.1 1), becomes:

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 IDEAL-GAS MIXTURES

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 FUGACITY AND FUGACITY COEFFICIENT: PURE SPECIES

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 VaporILiquid Equilibrium for Pure Species

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 FUGACITY AND FUGACITY COEFFICIENT:
SPECIES IN SOLUTION

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 Fugacity Coefficients from the Virial Equation of State

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GENERALIZED CORRELATIONS FOR THE FUGACITY COEFFICIENT

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 THE IDEAL SOLUTION

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 The Lewis Randall Rule

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 1 1.9 EXCESS PROPERTIES

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 The Excess Gibbs Energy and the Activity Coefficient

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 Chapter 12

Solution Thermodynamics:
Applications

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 LIQUID-PHASE PROPERTIES FROM VLE DATA

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 Activity Coefficient

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One-Parameter MARGULES Equation

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Two-Parameters MARGULES Equation

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Example of
Margules Equation

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Van Laar Equation for Activity
Coefficient Model

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Wilson's Equation for Activity
Coefficient

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NRTL Equation for Activity
Coefficient (3 parameters)

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 PROPERTY CHANGES OF MIXING

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 HEAT EFFECTS OF MIXING PROCESSES

Heats of Solution

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 THE REACTION COORDINATE

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 EFFECT OF TEMPERATURE ON THE EQUILIBRIUM CONSTANT

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