Thermodynamics

Biochemical Eng. Dept.
Thermodynamics
Thermodynamics
The word of Thermodynamics means heat power or power developed from heat. It is defined as the
science of energy includes the conversion of these energies from one form to another and their relationship
with properties of the system.
Units:
Fundamental units: e.g. length, mass, time, temperature … etc.
Derived units: e.g. area, velocity, acceleration, pressure … etc.
System of units:
C.G.S ; centimeter, gram, second (Absolute units)

F.P.S ; foot, pound, second (English engineering system units)
M.K.S ; meter, kg, second (SI units or International System of Units)
Laws of motion:
Newton’s 1st law of motion: every body continues in its state of rest or uniform motion in a straight line unless
it is acted by some external force.
Newton’s 2nd Law of Motion: F = ma (N)
Where: F = force, m = mass of body, a = acceleration

ma
In English units F = (lbf)
gc
lbm ft
Where gc is dimensional proportionality constant or gravitational constant = 32.174 , lbf = 4.448 N
lb f s 2
In SI units gc = 1 kg.m/N.s2
Newton’s 3rd Law of Motion: To every action there is always an equal and opposite action.
Ex: what is the force will given a mass of 250 kg with acceleration of 10 m/s?
Solution: F = ma = 250 × 10 = 2500 N
H.W.: A 15 kg steel container has 1.75 kmoles of liquid propane inside. A force of 2 kN now accelerates this
system. What is the acceleration?
Temperature: It is a measure of the molecular activity of a substance. The greater the movement of
molecules, the higher the temperature. There are two standard temperature scales normally employed for
measurement purposes are the Fahrenheit (F) and Celsius (C) scales and there are two absolute temperature
scales Kelvin (K) scale; corresponds to Celsius scale, and Rankine (R) scale; corresponds to Fahrenheit
scale.
°F = 32.0 + 1.8 ×oC

T(K] = T(°C) + 273 , T(R) = °F + 460
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Biochemical Eng. Dept. Thermodynamics
Volume,V: It is a quantity representing the product of three lengths. Specific volume or molar volume is a
volume per unit mass or mole.
Density, ρ: is the reciprocal of specific volume or molar volume.
Mole, mol: The measure of the amount of substance, defined as the amount of substance represented by as
many elementary entities.
Pressure, P: The pressure of a fluid is defined as a normal force exerted by a fluid per unit area.
F
P (N/m2) or Pascal (Pa); in SI units, or pound force per square inch (psi); in English units.
A
F mg Ahg
P    hρg
A A A
Pgage = Pabs - Patm
Pvac = Patm - Pabs

Where: Pgage = gage pressure, Pabs = absolute pressure, Patm = atmosphere pressure, Pvac = vacuum pressure.
Ex: A vacuum gage connected to a chamber reads 5.8 psi at a location where the atmospheric pressure is 14.5
psi. Determine the absolute pressure in the chamber.
Pabs = Patm - Pvac = 14.5 - 5.8 = 8.7 psi
Ex: A manometer is used to measure the pressure in a tank. The fluid used has a specific gravity of 0.85,
and the manometer column height is 55 cm, as shown in Fig. below. If the local atmospheric pressure is 96
kPa, determine the absolute pressure within the tank.
Solution: Pabs =Pgage + Patm

Pgage = hρg , but ρ = SG × ρH2O = 0.85 × 1000 = 850 kg/m3
Pgage = 0.55 m × 850 kg/m3 × 9.81 m/s2 = 4586 N/m2 = 4586 Pa = 4.6 kPa
 Pabs = 4.6 + 96 = 100.6 kPa
Work: Work W is done whenever a force acts through a distance.
dW = Fdl where F = force and dl = displacement
Consider a compression or expansion of fluid in a cylinder:

2
V
P = F/A → F = PA , V = Al → dV = Adl or dl = d
A
V
 dW = Fdl = PA d
A
V2
Since A is constant  dW = PdV →W=  PdV
V1
Energy: It is defined as the capacity of a system to perform work or produce heat.
Forms of energy: mechanical, electrical, chemical, heat, light ….. etc.
Kinetic energy: (EK) is the energy of motion.
dW = Fdl = ma dl , but a = du/dt
du dl
dW = m dl  m du but u = dl/dt
dt dt
u 22  u12
→ dW = mu du → W = m( )
2
 mu 2 
Or W =  EK = 
 
 2 
1
So the kinetic energy EK = mu 2 (N.m) or Joules
2
1
In English unit EK = mu 2 /gc (ft.lbf)
2
Ex: Determine the kinetic energy of 7 lbm of steam flowing through a pipe at a velocity of 100 ft/sec.
1 7lbm  100 ft / s
Solution: EK = mu 2 /gc = = 1088 ft.lbf
2 2  32.17 lbm ft / lb f s
Potential energy: EP is defined as the energy of position.
The minimum work required to raise the body of m mass from level z1 to z2 is
W = Fdl =F(z2 – z1) = mg(z2 – z1)
Or W =  Ep =  (mzg)
Thus EP = mzg (N.m) or Joules
In English unit EP = mzg/gc (ft.lbf)
Ex: Determine the potential energy of 50 lbm of water in a storage tank 100 ft above the ground.
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50 lbm  100 ft  32.17 ft / s 2

Solution: EP = mzg/gc = = 5000 ft.lbf
32.17 lbm . ft / lb f s 2
Note: For a freely falling body :  EK +  EP = 0
Heat: Heat (Q), like work, is energy in transit. The transfer of energy as heat, however, occurs at the
molecular level as a result of a temperature difference. The unit of heat is Joule (in SI units) or calorie or
BTU in English units.
BTU (British thermal unit) 1 BTU = 1055 J 1 calorie = 4.184 J
Internal energy (U): It is a microscopic forms of energy include those due to the rotation, vibration,
translation, and interactions among the molecules of a substance and has units of J or BTU.
U
The specific internal energy u = where m is the mass of substance.
m
Enthalpy (H): It is a heat content and total heat where it is a combination property:
H = U + PV
Flow Energy: It is the energy required to force the substance in the system or to remove it from the system.
FE = force × distance = F× L (N.m)
F = PA → FE = P.A.L = P.V
Zeroth law of thermodynamics: states that if two bodies are in thermal

equilibrium with a third body, they are also in thermal equilibrium with each other.
First law of thermodynamics: The energy can neither be created nor destroyed but rather transformed
into various forms.
Thermodynamics System:
System: It is a definite area or the space where some thermodynamics process is take place.
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Boundary: The envelope (Real or imaginary) which contains the system.
Surrounding: It is any thing out of the system.
Closed system: It is a region that of constant mass and no mass

can cross its boundary but energy, in the form of heat or work, can
cross the boundary.
Open system: It is a region in which the mass is not necessarily constant (mass flow) besides the mass as
well as the energy transfer cross its boundary.
Cv = control volume
Open
system
Isolated System: It is a system in which neither mass nor energy are allowed to cross the boundary.
State function: e.g. temp., pressure, volume, density, conductivity, viscosity, internal energy,
enthalpy ... etc. where depend on the initial and final conditions, represented by points on graph and when
T2 U2
integrated lead to finite difference. i.e.  dT = T2 – T1 and  dU  U

U1
2  U1
T1
Path function: e.g. Q , W which depend on the path, cannot represented by points on
graph but rather by area and when integrated lead to finite quantity but not finite
difference.
 dQ  Q and  dW W
T
State function path function
 dW W = P(V2 – V1)
Properties of a system:
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Intensive properties: are those that are independent of the mass of a system, such as temperature, pressure,
and density.
Extensive properties: The properties whose values for entire system are equal to sum of their values for
individual parts of the system and depend on the mass of the system. e.g. volume, mass, internal energy and
enthalpy.
Note: specific or molar extensive property (e.g. molar enthalpy) is intensive property.
M 1/2M 1/2M
Extensive property
V 1/2V 1/2V
P P P
T T T
Intensive
ρ ρ ρ
property
The formulation of 1st law of thermodynamics:
Δ (energy of the system) + Δ (energy of surrounding) = 0
Δ (energy of the system) = ΔU + ΔEK + ΔEP …..(1)
Δ (energy of surrounding) = ± Q ± W …..(2)
So summing 1 & 2 ΔU + ΔEK + ΔPK ± Q ± W = 0
Or ΔU + ΔEK + ΔEP = ± Q ± W
The sign of Q and W

+W +Q
-W -Q
Assume the total energy change of the system is equal to the heat added minus
work done by the system
i.e. ΔU + ΔEK + ΔEP = Q – W
For closed system there is no ΔEK and ΔEP , so the last Eqn. becomes
ΔU = Q – W (joules) in SI system but in English system (calorie, ft-lbf or BTU).
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The last Eqn is applied to the closed system (constant mass) i.e. non-flow process
Note: The total quantity of energy is constant, and when is disappears in one form it appears simultaneously
in other form.
Ex1: A rigid tank contains a hot fluid that is cooled while being stirred by a paddle wheel. Initially, the
internal energy of the fluid is 800 kJ. During the cooling process, the fluid loses 500 kJ of heat, and the
paddle wheel does 100 kJ of work on the fluid. Determine the final internal energy of the fluid. Neglect the
energy stored in the paddle wheel.
Solution: there is no ΔEK and ΔEP so ΔU = Q – W
U1 = 800 kJ , U2 = ? Q = - 500 kJ, W = - 100 kJ
Now U2 – 800 = -500 – (- 100)
→ U2 = 400 kJ
Ex2: When a system is taken from state a to state b in the figure below along path acb 100 J of heat flows
into the system and the system does 40 J of work. How much heat flows into the system along path aeb if the
work done by the system is 20 J? the system is return from b to a along the path bda. If the work on by the
system is 30 J, does the system absorb heat or liberate? How much?
Solution: Assume only internal energy is change in the system P
 ΔUab = Qacb – Wacb

b
→ ΔUab = 100 – 40 = 60 J
ΔUab = 60 = Qaeb – Waeb = Qaeb – 20 c d

e
→ Qaeb = 80 J
V
a
ΔUba = - ΔUab = Qbda - Wbda
- 60 = Qbda – (- 30)
→ Qbda = - 90 J [i.e. heat is liberate]
Enthalpy: Mathematically H = U + PV
Differentiation: dH = dU + d(PV)
Integration: ΔH = ΔU + Δ(PV)
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Steady state flow process:
Steady state is that circumstance in which there is no accumulation of mass or energy within the control
volume, and the properties at any point within the system are independent of time.
For sections 1 & 2 and unit mass of fluid:

u1
ΔU + ΔEK + ΔEP = Q – W ….(1)
Section1
1
ΔEK = u 2 per unit mass Heat
2
ΔEP = gΔz per unit mass z1 Q exchanger
Section2
Turbine
1
 ΔU + 2 u 2 + gΔz = Q – W …(2) u2
The total work of the system W is equal to z2

the work done on the system at section 1 ,
work done by the system at section 2 and
Ws
the shaft work, Ws .
i.e. W = Ws + W1 + W2
W1 = -P1V1 and W2 =P2V2
 Eqn (2) becomes

1
ΔU + u 2 + gΔz = Q – (Ws + P2V2 – P1V1)
2
1
Or ΔU +Δ(PV) + u 2 + gΔz = Q – Ws
2
But ΔH = ΔU + Δ(PV)
1
 ΔH + 2
u 2 + gΔz = Q – Ws
This equation is the mathematical expression of the 1st law for a steady flow process and per unit mass of
fluid.
u 2 g
In English system ΔH +
2gc
+ gc Δz = Q – Ws
Note: H, Q are in BTU but EK , EP and W in ft.lbf so the units in Eqn above must be corrected by the factor
ft.lb f
778.16
BTU
Ex: Air at 1 bar and 25oC enters a compressor at low velocity, discharges at 3 bar, and enters a nozzle in
which it expands to a final velocity of 600 m/s at the initial conditions of pressure and temperature. If the
work of compressor is 240 kJ per kg of air, how much heat must be removed during compression?
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Solution:
Air 1bar, Air 1 bar,

Air 3bar, 25oC, 600m/s
25oC
Compressor Nozzle
Section 1 Section 2
Ws
1
ΔH + u 2 + gΔz = Q – Ws
2
Since the air is return to the initial conditions of T & P so the ΔH = 0 (state function) and no information
about potential energy (or the air at the same level in section 1 & 2) so gΔz = 0.
1 2
u1 = 0 so the above Eqn is reduce to u 2 = Q – Ws
2
u2 = 600 m/s , Ws = - 240 kJ/kg
→ ½ (600)2 = Q + 240000
→ Q = - 60000 J/kg or Q = - 60 kJ/kg
Ex: Water at 200oF is pumped from a storage tank at the rate of 50 gal/min. The motor
for the pump supplies
work at the rate of 2 hp. The water passes through a heat exchanger, where it
gives up heat at the rate of
40000 BTU/min and is delivered to a second storage tank at an elevation 50 ft above
the 1st tank. What is the
temperature of the water delivered to a second tank?
Section 2
Solution: For sections 1 & 2:
u 2 g
ΔH + 2gc
+ gc Δz = Q – Ws ……(*) Tank2
Negligible the velocity in sections 1 & 2, i.e.

Section 1
u 2
Q
=0
2gc pump
Tank1 Heat exchanger
The Eqn (*)ìs applied per unit mass
Ws
1 ft3 = 7.48 gal and density of water at 200oF ρH2O = 60.1 lbm/ft3
gal 1 ft 3 lb
So the mass flow is 50   60.1 m3 = 402 lbm/min
min 7.48 gal ft
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42.41BTu / min
1 hp = 42.41 BTU/min → Ws = - 2 hp× /402 lbm /min = - 0.21 BTU/lbm
hp
Q = - 40000 BTU/min/402 lbm/min = - 99.5 BTU/lbm
32.17 50
Now Eqn (*) becomes: ΔH + = - 99.5 + 0.21
32.17 778.16
→ ΔH = - 99.35 BTU/lbm
The enthalpy of water at 200oF is H1 = 168.09 BTU/lbm
ΔH = H2 – H1 = -99.35 = H2 – 168.09
→H2 = 68.47 BTU/lbm
From steam table at H = 68.47 BTU/lbm , T = 100.74oF
The Reversible Process:
A process is reversible when its direction can be reversed at any point by an infinitesimal change in external
conditions. So it is idealized process, not occur in nature and can never be achieved.
You may be wondering, then, why we are bothering with such fictitious processes. There are two
reasons:
First, they are easy to analyze, since a system passes through a series of equilibrium
states during a reversible process; second, they serve as idealized models to which
actual processes can be compared.
Irreversible process: It is the process which carried out in finite time with real
substance and accompanied in some degree by dissipative effects of one kind or
other.
Notation; constant-volume and constant-pressure processes:
For closed system of n moles the 1st law of thermodynamics is written as:
d(nU) = dQ – dW …… (1)
The W for mechanically, reversible, non-flow process is
dW = Pd(nV)
Eqn (1) becomes d(nU) = dQ –P d(nV) …..(2)
at constant volume d(nV) = 0
 Eqn (2) becomes: d(nU) = dQ
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Or Q = n ΔU (const. V)
From enthalpy definition and for n moles
nH = nU + P(nV)
Differentiation at const. P → d(nH) =d(nU) + Pd(nV) .....(3)
Subsititute Eqn (2) in (3) → d(nH) = dQ – Pd(nV) + Pd(nV)
 d(nH) = dQ or Q = nΔH (const. P)
Heat capacity:
It is the ratio of the heat (Q) added to or removed from a substance to the change in temperature ( T)
produced.
dQ
So: C= , C likes Q , is path function (path-dependent quantity).
dT
 U 
Heat capacity at constant volume: CV =  
 T  V
 H 
Heat capacity at constant pressure: CP =  
 P  P
The molar heat capacity and specific heat capacity (usually called specific heat) depending whether U or H
are molar or specific properties.
At constant volume dU = CV dT
Integration → ΔU = CV ΔT per unit mole or per unit mass (const. V)
At constant pressure dH = CP dT
Integration → ΔH = CP ΔT per unit mole or per unit mass (const. P)
Equilibrium: is a word denoting a static condition, the absence of change. In thermodynamics it taken to
mean not only the absence of change but the absence of any tendency toward change on a macroscopic scale.
Hence a system at equilibrium may be described as one in which all forces are in exact balance.
The phase rule: F = 2 – π + N

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Where: F is the degree of freedom: independent intensive variables [number of independent variables that
must be fixed to establish the intensive state of the system]
π: number of phases
N: number of species
Ex: How many degree of freedom has each of the following system?
(1) Liquid water in equilibrium with its vapor.

(2) Liquid water in equilibrium with a mixture of a water vapor and nitrogen.
(3) A liquid solution of alcohol in water in equilibrium with its vapor.
Solution: F = 2 – π + N
(1) π = 2, N = 1 → F = 2 – 2 +1 = 1
This means a one variable must be known (temp. or pressure) so as to know the other
variable. Or it must be know the pressure only to know the boiling point temperature.
(2) π = 2, N = 2 → F = 2 – 2 + 2 = 2
(3) π = 2, N = 2 → F = 2 – 2 + 2 = 2
P
The PVT behavior of pure substance
The diagram below is often called the phase

diagram since all three phases are separated
from each other by three lines.
Critical point: i.e. critical temperature and

critical pressure TC and PC (maximum temp.
and maximum pressure) that the liquid and
gas can exist in equilibrium.
Triple point: That is, all three phases of Pure

substance coexist in equilibrium.
For water, the triple-point temperature and
pressure are 0.01°C and 0.6117 kPa.
T
Relation of V, P, T: Any variable of the three is a function of two other variables. e.g. V = f(T,P) and
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 V   V 
dV    dT    dP …..(1)
 T P  P  T
For liquids they are two properties:
1  V 
1- The volume expansivity     ……….(2)
V  T  P
1  V 
2- The isothermal compressibility k    ……....(3)
V  P  T
dV
Substitute Eqns 2 & 3 in 1 →   dT  kdP ………(4)
V
For real liquids  and k are weakly functions of temp and pressure.
V2
Integrated Eqn 4 → ln   (T2  T1 )  k ( P2  P1 )
V1
Ex: For acetone at 20oC and 1 bar,  = 1.487×10-3 oC-1

k = 62×10-4 bar-1
V = 1.287 cm3/g
Find:
 P 
1) The value of  
 T V
2) The pressure generated when acetone is heated at constant volume from 20 oC
and 1 bar to 30oC.
3) The volume change when acetone changed from 20 oC and 1 bar to 0oC and 10
bar.
Solution:
dV
(1) At constant volume i.e.   dT  kdP = 0
V
 P   1.487  10 3
→ dT  kdP →   = = = 24 bar/oC
 T V k 62  10 6
(2) Assume β and k are constant for 10oC change, so

Integration of dT  kdP → P  T = 24(30 – 20) = 240 bar
k
And P2 = P1+ ΔP = 1 + 240 =241 bar
V2
(3) ln   (T2  T1 )  k ( P2  P1 ) = 1.487×10-3(30 – 20) - 62×10-4 (241 – 1 ) = - 0.0303
V1
V2
= 0.9702 → V2 = 0.9702×1.28 = 1.25 cm 3/g → ΔV = V2 – V1 = 1.25 – 1.28 = -
V1
0.03 cm3/g
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The ideal gas:
Ideal gas Real gas

1- No force attraction between the molecules. 1- There is force attraction between molecules.
2- Volume of molecules is small compared with the 2- The volume of molecules is not negligible.
total volume (i.e. negligible volume of molecules) 3- The pressure is more the 3 bars.
3- The pressure must not be more than 3 bars. 4- There are more than 100 equations of state express
4- The equation of state is simple: PV = nRT the PVT relation; PV = ZnRT where Z ≠ 1
Thermodynamics relationships for ideal gas:
1- The constant-volume (Isocharic) process: for mechanically reversible constant-volume non-flow

process and for one mole:
dU = dQ = CV dT ……….(1)
For a finite change, ΔU = Q =  CV dT

U & CV are functions of T.
Note: always ΔU = C V dT regardless of the kind of process, but at constant V only Q = ΔU.
2- The constant pressure (Isobaric) process: for mechanically reversible,

constant-pressure, non-flow process and for one mole:
dH = dQ = CP dT ……..(2)
and
ΔH = Q =  C P dT
H & CP are functions of T
Note: always ΔH = C P dT for all finite processes, but at constant P only Q = ΔH.
The relation between CV & CP:
H = U + PV , but PV = RT (V is molar volume)
So H = U + RT and dH = dU + RdT
From Eqns 1 & 2: CP dT = CV dT + RdT
and CP = CV + R
3- The constant-temperature (Isothermal) process:
dU = CV dT (but T is constant) for mechanically reversible, constant-pressure, non-

flow process dU = 0
14
and dU = dQ – dW = 0
→ Q – W = 0 or Q = W =  PdV =
since for ideal gas PV = RT or P = RT/V
dV
→ Q = W =  RT
V
V2
Integral between V1 and V2 → Q = W =RT ln
V1
At constant T P1V1 = P2V2
P1
→ Q = W =RT ln
P2
4- Adiabatic process: It is one for which there is no heat transfer between the
system and its surrounding; i.e. dQ = 0 . Applied 1st law for mechanically reversible,
adiabatic, non-flow process and for one mole:
dU = - dW = - PdV , but dU = CV dT and P = RT/V
dV dT R dV
→ CV dT = - RT →  ............(3)
V T CV V
CP
The ratio   and CP = CV + R
CV
CV  R R R
→ γ= = 1+ or = γ – 1 substitute in Eqn (3)
CV CV CV
dT dV
→  (  1)
T V
T2 V
For γ constant → ln  (  1) ln 2
T1 V1
 1
T2  V1 
Take exponential →   ..…..(4)
T1  V2 
Since P1V1/T1 = P2V2/T2 eliminate from V1/V2 in Eqn 4:
( 1) / 
T2  P2 
  ……..(5)
T1  P1 
Equating Eqn 4 and 5:
 1 ( 1) / 
 V1  P 
→   =  2  → P1V1γ = P2V2 γ = PV γ = constant ……….(6)
 V2   P1 
The work of the adiabatic process may be obtained from the relation:
15
- dW = dU = CV dT for constant CV, integration gives:
R
W = ΔU = - CV ΔT but CV =   1
RT1  RT2
 R T
→ W= = but RT1 = P1V1 and RT2 = P2V2
 1  1
P V  P2V2
→ W= 1 1 If V2 is not known, substituted from Eqn 6:
 1
( 1) /  ( 1) / 
P1V1   P2   RT1  P  
→ W= 1     = 1   2  
  1   P1    1   P1  
   
Note: for adiabatic processes but not mechanically reversible are not described by these equations.
For real gases which are not great deviation, for monatomic gases γ = 1.67, for diatomic gases γ = 1.4 and for
polyatomic gases γ = 1.3 such as CO2 , SO2 , NH3 , and CH4
5- The polytropic process: This is the general case which no specific condition other than mechanically
reversibility are imposed.
For mechanically reversible non-flow process and one mole of ideal gas:
dU = dQ – dW → ΔU = Q – W (1st law)
W =  PdV , ΔU =  CV dT , ΔH =  CP dT ,
And for Q is obtained from 1st law.
Q=  CV dT +  PdV
Ex: An ideal gas undergoes the following sequence of mechanically reversible process:
(a) From initial state of 70oC and 1 bar, it is compressed adiabatically to 150oC.
(b)It is then cooled from 150oC to 70oC at constant pressure.
(c) Finally it is expanded isothermally to its original state.
Calculate W, Q, ΔU and ΔH for each of three processes and for the entire cycle. Take CV
= (3/2)R and
CP = (5/2)R.
If these processes are carried out irreversible, calculate Q, W for 80% efficiency.
Solution: (1) Reversible process
CV = (3/2)R = (3/2) × 8.314 = 12.471 J/mol.K and CP = (5/2)R = (5/20) × 8.341 = 20.785 J/mol.K
16
Assume 1 mole (as basis) of gas.

(a) Adiabatically, i.e. Q = 0 → from 1st law ΔU = – W = nCV ΔT = 1×12.471(150 – 70) =
998 J
ΔH = nCP ΔT = 1×20.785 (150 – 70) = 1663 J
(b) Constant P.
→ ΔH = Q = nCP ΔT = 1×20.785 (70 – 150) = -1663 J
ΔU = nCV ΔT = 1×12.471(70 – 150) = - 998 J P b

3 2 150oC
70oC
ΔU = Q – W → W = Q – ΔU = -1663 – (-998) = - 665 J a
c
(c) Isothermal, i.e. ΔT = 0
1
 ΔU = 0 and ΔH = 0 70oC
P1 P3 V
From 1st law 0 = Q – W or Q = W = nRT ln = nRT ln
P2 P1
P1 = 1 bar, P3 = P2 (case b) but P2 is found from case a, i.e. adiabatically
 /( 1)
 T2 
 
T
P2 = P1  1  , γ = CP /CV = 20.785/12.471 = 1.667
1.667 / 0.667
 150  273 
 P2 = 1   = 1.69 bar = P3
 70  273 
P3
 Q = W = nRT ln
P1
= 1×8.341× (70 + 273) ln 1.69/1 = 1495 J
For the entire process: Q = 0 – 1663 + 1495 = - 168 J
W = - 998 – 998 + 1495 = - 168 J
ΔU = 998 – 998 + 0 = 0
ΔH = 1663 – 1663 + 0 = 0
(2) Irreversible process
(a) This step cannot be adiabatic: ΔU = nCV ΔT = 1×12.471 (150 – 70) = 998 J = ΔUirr
Wr  998
Wir = = = - 1248 J → Q = ΔU + W = 998 – 1248 = - 250 J
 0.8
 665
(b) ΔUrev = ΔUirr = - 998 , Wirr = = - 831 J → Q = - 998 – 831 = - 1829 J
0.8
17
(c) Isothermally expansion , i.e. ΔU = 0 , Wirr < Wrev → Wirr = Wrev × η = 1495×0.8 =
1196 J
Q = ΔU + W = 0 + 1196 = 1196 J
For the entire process ΔU and ΔH are zero.
Q = - 250 – 1829 + 1196 = - 883 J
W =- 1248 – 831 + 1196 = - 883 J
Note: the process in the reversible and irreversible are requires work and produce the
same amount of heat, but in the irreversible process the work is five times of the work
in the irreversible process though η = 0.8.
Compressibility factor:
The state equation of real gas is PV = ZRT where Z is compressibility factor.

There are many equations to calculate Z:
PV BP
Virial equation: Z
RT
 1
RT
for P < 15 bar.
PV B C
Z  1  2 for P < 50 bar.
RT V V
Where B is second Virial coefficient and C is third Virial coefficient which they are
function of T only.
Pitzer and coworkers correlation:
Z = Zo + ωZ1 where Zo and Z1 are complex functions of Tr and Pr and are found from
figures (3.12 – 3.15).
ω is acentric factor and is found in Appendix B, page 571.
T P
Tr = = reduce temp. and Pr = = reduce pressure, TC and PC are found in
TC PC
Appendix B, page 571.
Ex: Determine the molar volume of n-butane at 510 K and 25 bar by the following
equations:
(1) The ideal gas Eqn.

(2) The generalized compressibility factor Eqn.
18
RT 8.314  510
Solution: (1) PV = RT → V  = = 0.0016961 m3/mol = 1696.1 cm3/mol
P 25  10 5
(2) Z = Zo + ωZ1 , from App. B for (n-butane) Tc = 425.2 K, Pc = 38 bar and ω = 0.193
T P
→ Tr = = 510/425.2 = 1.2 , Pr = = 25/38 = 0.658
TC PC
From Fig. (3.12) Zo = 0.865 and from Fig.(3.14) Z1 = 0.038

 Z = 0.865 + 0.193×0.038 = 0.872
 V = ZRT/P = 0.872×8.314×510/2500000 = 0.001479 m3/mol = 1479 cm3/mol
Generalized correlations for liquids:
The following Eqn is proposed by Rackett:
0.2857
Vsat = Vc Z c(1Tr )
To estimate the volume of the liquid at pressure:
Vc  r1
V= or V2  V1
r r2
Where: V2 = required volume

V1 = known volume
ρ = reduce density read from Fig 3.17
Ex: (a) Estimate the molar volume of the saturated liquid ammonia at 310 K.
(b) Estimate the molar volume of the saturated liquid ammonia at 310 K and 100 bar.
0.2857
Solution: (a) Vsat = Vc Z c(1Tr )
From App. B Tc = 405.6 K, Pc = 112.8 bar, Vc = 72.5 cm3/mol, Zc = 0.242

0.2857
And Tr = T/Tc = 310/405.6 = 0.764 → Vsat =72.5× 0.242 (10.764 ) = 28.35
cm /mol
3
(b) Tr = 0.764, Pr = 100/112.8 = 0.887
 From Fig 3.17 ρr = 2.38
Vc
→ V= = 72.5/2.38 = 30.5 cm3/mol
r
19
Temperature effect on heat capacity:
CP for ideal gas may calculated graphically

as a function of T as shown in the figure.
Or CP for ideal gas may calculated analytically as
ig
C Pig
C P R
R = A + BT + CT2 + DT-2
Where A, B, C, and D are constants for each substance and are tabulated in table (4.1).
T2
ΔH = C
T1
P dT T
ig
Mean heat capacity C Pmh :
ig
C Pmh C D
 A  BTam  (4Tam
2
 T1T2 ) 
R 3 T1T2
Where: Tam is arithmetic mean temp. = (T1 + T2)/2
H
ig
ΔH = C Pmh (T2 – T1) And T2   T1
C ig
pmh
Ex: Calculate the heat required to raise the temperature of 1 mol of methane from 260 oC to 600oC in a flow
process at a pressure of approximately 1 bar.
ig
Solution: Q = ΔH = C Pmh (T2 – T1) [const. P]
ig
C Pmh C D
2
 T1T2 ) 
R 3 T1T2
T1 = 260 + 273 = 533 K , T2 = 600 + 273 = 873 K
Tam = (533 + 873)/2 = 703 K
From Table 4.1 for methane gas: A = 1.702, B = 9.082×10-3 , C = -2.164×10-6
ig 2.164  10 3
C Pmh /R = 1.702 + 9.082×10-3(703) - [4×(703)2 - 533×873] = 6.996
3
20
ig
→ C Pmh = 6.996×8.314 = 58.165
Q = ΔH = 58.165 (873 – 533) = 19780 J
Ex: What is the final temperature when 0.4×10 6 Btu are added to 25 lbmol of ammonia initially at 500 oF in a
steady state flow process at approximately 1 atm.
u 2 g
Solution: For steady flow process nΔH + n + n g ΔZ = Q – Ws
2gc c
No Ws , no ΔZ , no Δu2 → nΔH = Q → ΔH =Q/n
1055 J 1mol 500

Q =0.4×106 Btu × = 422 ×106 J , n = 25 lbmol× 2.2 lbmol = 11.36 mol , T(oC) = - 32 =
1Btu 1.8
260oC
 ΔH = 422 ×106/11.36 = 37.148×106 J/mol
H
T2   T1 , T1 = 260+273 = 533 K
C ig
pmh
533  T2
Tam = ……(1)
2
ig 0.186  10 5
C Pmh = 8.314(3.578 +3.02×10-3Tam - ) ….(2)
T1T2
Iteration between Eqn 1 & 2 start with T2 ≥ T1 → T2 = 1250.1 K
Mixture heat capacity: The molar heat capacity of the mixture in the ideal gas
state is
C igpmixture  y A C igpA  y B C igpB  y C C PigC
The latent heat accompanying phase changes: such as heat of fusion and heat
of vaporization.
dP sat
ΔH = T ΔV (Clapeyron equation)
dT
Where: ΔH = latent heat
ΔV = volume change accompanying phase change.
Psat = vapor pressure
Latent heat of vaporization at normal boiling point:
21
H n / Tn 1.092(ln PC  1.013)

R 0.93  Trn
Where: Tn = normal boiling point
ΔHn = molar latent of vaporization at Tn
Pc = critical pressure, bar
Trn = reduced temperature at Tn
Ex: What is the latent heat of vaporization of water at normal boiling point?
H n / Tn 1.092(ln PC  1.013)
Solution: 
R 0.93  Trn
Tn = 100oC = 373.15 K,
PC = 220.5 bar , TC = 647.3 K (appendix B) and Trn = 373.15/647.3 = 0.577
1.092(ln 220.5  1.013)

 ΔHn =  8.314  373.15 = 41940 J/mol
0.93  0.577
0.38
H 2  1  Tr 2 
Latent heat at temperature:  
H 1  1  Tr1 
Standard heat of reaction: It is the enthalpy change that appears directly as a result of a reaction.
Standard heat of formation: It is a special heat of reaction for the formation of the 1 mole of a
component from its constituent elements in standard state (1 bar, 25oC).
e.g. C(s) + O2(g) → CO2 (g) H of 298 = -393.509 J
H2 (g) since H2 is element H of 298 = 0
So heat of formation of elements at standard state = 0
H2O + SO3 → H2SO3 is not formation reaction.
Standard heat of formation are tabulated in table (4.4)
Ex: Calculate the standard heat at 25oC for the following reaction
4HCl(g) + O2(g) → 2H2O(g) + 2Cl2(g)
Solution:
H 298
o
=    H 
i i
o
prd -    H  rec
i i
o
22
Where:  i is stoichiometric coefficient
From table (4.4) H 298

o
for H2O(g) = - 241818 J/mol, for HCl = - 92307 J/mol
 H 298
o = 2(- 241818) – 4(- 92307) = - 114 408 J/mol
The standard heat of combustion: It is a heat accompanying to the reaction between an element or
compound and oxygen to form specified combustion products.
e.g. 4C(s) + 4O2(g) → 4CO2(g) H 298

o
= 4 (- 393509)
Effect of temperature on standard heat of reaction: To evaluate heat of

reaction at any temperature:
B 2 C 3 D
I= H 298
o
- R(ΔAT + T + T - ) ….(1) T = 289 K
2 3 T
B 2 C 3 D
H To = I + R(ΔAT + T + T - ) ….(2) at any T
2 3 T
Ex: Calculate heat of methanol synthesis reaction at 800oC:
CO(g) + 2H2(g) → CH3OH(g)
Solution: From Tab. 4.4 heat of formation for CO(g), H 298

o
= -110525 J and for CH 3OH,
H 298 = -200660 J
o
For the reaction H 298

o
= -200660 – (-110525) = - 90135 J
The value of constants A, B, C, and D are found from tab 4.1
i C×10 D×10-
i A B×103 6 5
2.21
1 12.21 0
CH3OH 1 -3.45
6
3.37 -
CO -1 0
6 0.557 0.031
H2 -2 0
3.24 0.422 0.083
9
ΔA = 2.211 – 3.376 -2(3.249) = - 7.663
23
ΔB = 12.216×10-3 – 0.557×10-3 – 2(0.422×10-3) = 10.815×10-3
By the same way ΔC = - 3.45×10-6 and ΔD = - 0.135×105
Substitute these values in equation (1) above and T = 298 K
10.815  10 3  3.45  10 6
I = - 90135 – 8.314[ - 7.663(298) + ×298 + ×2983 -
2 3
 0.135  10 5
]
298
= - 75259 J
By using Eq. 2 with T = 800 + 273 = 1073 K
10.815  10 3  3.45  10 6
H 1073
o
= -75259 + 8.314[- 7.663(1073) + ×1073 + ×10733 -
2 3
 0.135  10 5
]
1073
H 1073
o
= - 103566 J
Adiabatic flame temperature: It is the maximum theoretical flame temperature

which achieved at adiabatic condition.
i.e. Q = 0 = ΔH = H 298
o
+ H Po
Ex: What is the maximum temperature that can be reached by the combustion of
methane with 20 % excess air? Both the methane and air enter the burner at 25oC.
Solution: The reaction is CH4 + 2O2 → CO2 + 2H2O(g)

products at
1 bar and T2o C
Assume adiabatic reaction and complete combustion: 1 mol CO2
2 mol H2O
So ΔH = H 298
o
+ H Po = 0 → H Po = - H 298
o
0.4 mol O2
9.03 mol N2
H 298
o Reactants
= - 393509 + 2(-241818) – (-74520) = - 802625 J at o
1 bar and 25 C
1 mol CH4
For 1 mole of methane as the basis: 2.4 mol O2
9.03 mol N2
Moles O2 required: 2.0
Moles excess O2: 0.2×2 = 0.4 → total mole O2 enter = 2.4
21
Moles N2 entering = 2.4× = 9.03
79
Products output: O2 = 0.4 moles, N2 = 9.03 moles, H2O = 2 moles and CO2 = 1 mole
24
802625
H Po = n C i
o
Pmh (T2 – T1) → T2 =
 ni C Pmh
o + 298 …(1)
n C i
o
Pmh P = R[  ni Ai +(  ni Bi )+  ni C i /3 (4T2 am – T1T2) +
n D
i i
]
T1T2
From tab.4.1 n A i i = 5.457 + 2(3.47) + 0.4(3.639) + 9.03(3.28) = 43.489
Similarly for n B i i = 9.502×10-3
n D i i = -0.645×105 where Ci = 0 for all products
 0.645  10 5
Whence  ni C Pmh
o
P = 8.314[43.489 + 9.502×10 Tam -3
+ ] ....(2)
T1T2
Assume T2 ≥ T1 and ittration between equation 1 and 2 → T2 = 2066 K
H.W. Resolve the the above example with (1) conversion of 80%. (2) amount of CH 4
750 moles
Second Law of thermodynamics

It is impossible by a cyclic process to convert the heat absorbed by a system
completely into work.
But can be convert the work completely into heat.
Heat engine: It is a device or machine that produces work from heat in a cyclic
process, such as steam power plant.
 = Wnet where: Wnet = net work output, Qabs = heat input or absorbed = QH
Qabs
Wnet = Q H  QC where: QH = heat absorb from a hot reservoir, QC = heat

discards to a cold reservoir.
QH  QC QC
→  =1-
QH QH
Carnot Engine: It is ideal reversible engine that condition for converting heat into
work with maximum efficiency, where:
1) The cycle must consists of a service of a processes each of while is fully reversible.
2) All heat reception occurs at a maximum cycle temperature and all heat rejection
occurs at the minimum cycle temperature.
25
The Carnot cycle is composed of four reversible processes—two isothermal and two
adiabatic—and it can be executed either in a closed or a steady-flow system.
a. Reversible Isothermal Expansion (process 1-2, TH, constant).

Where the heat QH is absorbed from hot reservoir
V2
QH = RTmax ln
V1
b. Reversible Adiabatic Expansion (process 2-3, temperature drops from TH to TC).
 
P2 T   1  Tmax   1
  2  = 
T 

Tmax =TH, Tmin =TC
P3  T3   min 
1 
V2  T   1  Tmax   1
Or   2  =  

V3  T3   Tmin 
c. Reversible Isothermal Compression (process 3-4, TC , constant). Where the heat QC is

rejected to cold reservoir.
V3
QC = RTmin ln
V4
d. Reversible Adiabatic Compression (process 4-1, temperature rises from TC to TH).
 
P1 T   1  Tmax   1
  1  =  

P4  T4   Tmin 
QH TH QC TC QC
 or  but  = 1-
QC TC QH TH QH
TC
→ =1- efficiency of ideal reversible process T in K and not in oC
TH
Ex: A Carnot heat engine, shown in figure below, receives 500 kJ of heat per cycle from a high-temperature
source at 652°C and rejects heat to a low-temperature sink at 30°C. Determine (a) the thermal efficiency of
this Carnot engine and (b) the amount of heat rejected to the sink per cycle.
26
TC 30  273
Solution: (a)  = 1 - =1- = 0.672
TH 652  273 TH=
That is, this Carnot heat engine converts 67.2 percent of the heat it receives to work.
TC 30  273
(b) QC = QH = ×500 = 164 kJ
TH 652  273
QL
Corollaries: TC=
(1) No heat engine operating between two heat reservoirs, each having a fixed temperature can be more
efficient than a reversible engine operating between the same temperatures.
(2) All reversible engines operating between two heat reservoirs each having own fixed temperature have the
same efficiency.
(3) The efficiency of each reversible engine operating between two reservoirs is independent on the nature of
the working fluid but depends on the temperature of the reservoirs.
Entropy, S, is a thermodynamic function; measure of molecular randomness used to determine the thermal
efficiency of engines and cycles and is defined in terms of a system undergoing a reversible process:
dQrev
dS  ….(*)
T
dQrev is a differential amount of heat being reversibly received or rejected at reservoir temperature, T, by a
reversible heat engine. If the reservoir temperature is a constant, then:
Qrev
S  For adiabatic reversible process ΔS = 0 (isentropic)
T
ΔSsyst + ΔSsurr ≥ 0 i.e. ΔStotal ≥ 0 where ΔS approaches zero for reversible process.
QH TH
For Carnot engine the equation:  may written as
QC TC
QH QC
 QH is positive value (absorbed) and QC is negative value (rejected).
TH TC
Q  QC Q H QC
 TH 
TC
or
TH

TC
=0
H
dQ H dQC
In differential term  =0
TH TC
27
Integration gives the sum of all quantities dQ/T for the entire cycle
dQrev
 T
=0
Entropy change of an ideal gas:
By the 1st law written for one mole or a unit mass of fluid: dU = dQ – dW
For a reversible process, this becomes: dU = dQrev – PdV …..(1)
By the definition of enthalpy: H = U + PV or dH = dU + PdV + VdP ….(2)
Substitute Eqn (1) in (2): dH = dQrev – PdV + PdV + VdP
Or dQrev = dH – VdP …..(3)
For an ideal gas, dH = C Pig dT and V = RT/P Eq. (3) then becomes
RT dQrev C Pig dP dQrev

dQrev = C Pig dT - dP or  dT  R but dS =
P T T P T
C Pig dP
So dS  dT  R Integration from T1 and P1 to T2 and P2
T P
T2 P
S  C Pig ln  R ln 2 For C Pig is constant and independent of temperature.
T1 P1
Or
T2 P
S  C Pms
ig
ln  R ln 2
T1 P1 For C Pig is dependent on temperature.
C igpms  D 
Where:  A  BTlm  TamTlm C  
R  (T1T2 ) 2 
T2  T1
Tlm is logarithmic mean temperature: Tlm 
ln(T2 / T1 )
If the body changes temperature as a result of exchanging heat, then for a reversible, constant pressure
process, dQrev = CpdT , and Eqn (*) becomes
T2
S P  C P ln
T1
Likewise, for a reversible constant volume heat exchange dQrev = CV dT:
T
SV  CV ln 2
T1
28
Ex: A heat source at 800 K loses 2000 kJ of heat to a sink at (a) 500 K and (b) 750 K. Determine which heat
transfer process is more irreversible.
Solution: ΔStotal = ΔSsource + ΔSsink
Q
(a) ΔSsource = = - 2000/800 = - 2.5 kJ/K
T
Q
ΔSsink = = 2000/500 = 4 kJ
T
 ΔStotal = -2.5 + 4 = 1.5 kJ/K
Q
(b) ΔSsource = = - 2000/800 = - 2.5 kJ/K
T
Q
ΔSsink = = 2000/750 = 2.7 kJ/K, ΔStotal = - 2.5 + 2.7 = 0.2 kJ/K
T
Since ΔStotal (a) > ΔStotal (b) → ΔStotal (a) is more irreversible process where ΔStotal for reversible process
approaches zero.
Ex: An inventor claims to have devised a process which takes in only saturated steam at 100 oC and which by
a complicated series of steps makes heat continuously available at a temperature level of 200 oC. He claims
further that for every kilogram of steam taken into the process 2000 kJ of energy as heat is liberated at the
higher temperature level of 200oC. Show whether or not this process is possible. In order to give the inventor
the benefit of any doubt, assume cooling water available in unlimited quantity at a temperature of 0oC.
Solution: Since the cooling water is available at 0oC, maximum use can be made of the steam by cooling it to
this temperature. We therefore assume that the steam is condensed and cooled to 0oC.
According to 1st law of thermodynamics for flow process:
ΔH + ½ Δu2 + gΔZ = Q – WS (no velocity change, no level change and no shaft work)
→ ΔH = Q Heat reservoir
200oC
From steam table:
H1 = 2676 kJ/kg, S1 = 7.3554 kJ/kg.K

2000 kJ
H2 = 0 and S2 = 0
Saturated steam at 100oC Liquid water at 0oC
Apparatus
H1 = 2676 kJ/kg H2 = 0
 ΔH = H2 – H1 = 0 – 2676 = - 2676 kJ/kg = Q
S1 = 7.3554 kJ/kg.K Qo S2 = 0
Q = -2000 + Qo = - 2676 → Qo = - 676 kJ/kg
For 1 kg of steam ΔS = S2 – S1 = 0 – 7.3554 = - 7.3554 kJ/kg.K
Q 2000 Heat reservoir 0oC

For the heat reservoir at 200oC ΔS = = = 4.227 kJ/kg.K
T 200  273 (cooling water)
676
For the heat reservoir at 0oC ΔS = = 2.475 kJ/kg.K
0  273
29
ΔStotal = – 7.3554 + 4.227 + 2.475 = - 0.6536 kJ/kg.K
Since the result is negative, i.e. it is violate the 2nd law of thermodynamics: ΔStotal ≥ 0
 The process is impossible
Third law of thermodynamics: The entropy of a pure crystalline substance at

absolute zero temperature is zero.
Relations among thermodynamic properties for a homogeneous

phase of constant composition
The 1st law for closed system of n moles:
d(nU) = dQ – dW
For reversible process: dWrev = Pd(nV) and dQrev = Td(nS) substitute in above Eq.
d(nU) = Td(nS) - Pd(nV) ….(1)
Eq. (1) applies to any process of constant mass and closed system (not restricted to
reversible process)
The enthalpy definition is
H = U + PV ….(2)
Two additional properties, are the Helmhotz energy,
A = U – TS …. (3)
And the Gibbs energy,
G = H – TS ….(4)
Multiplication of Eq. 2 by n and differentiation:
d(nH) = d(nU) + Pd(nV) + (nV)dP substitute d(nU) from Eq. 1
d(nH) = Td(nS) + (nV)dP ….(5)
Similarly for Eq. 3
d(nA) = d(nU) – Td(nS) – (nS)dT substitute d(nU) from Eq. 1
d(nA) = - Pd(nV) – (nS)dT ...(6)
Similarly for Eq. 4
d(nG) = (nV)dP – (nS)dT ....(7)

30
Eqs. 1, 5, 6, and 7 if they write to one mole (or to a unit mass):
dU = TdS – PdV ….(8)
dH = TdS + VdP ….(9)

Fundamentals property relations for a homogeneous fluid
dA = - PdV – SdT ….(10) of constant composition.
dG = VdP - SdT ….(11)
 F   F 
If F = F(x,y), then dF   x  dx   y  dy
 y  x
Or dF = Mdx + Ndy
 F   F 
M   and N   y 
 x  y  x
 M  2F  N  2F
For another differentiation:    and   
 y x xy  x  y xy
 M   N 
      …(12)
 y  x  x  y
So by similar to Eq. 12 , Eqs. 8 – 11 can be write as
…..(13)
…..(14)
…..(15)
….(16)
These are known as Maxwell equations.
Effect of P and T on H and S :
H = H(T,P) and S = S(T,P)
 H   H 
Derivation → dH    dT    dP ….(17)
 T  P  P  T
 S   S 
And dS    dT    dP …..(18)
 T  P  P  T
31
 H 
Heat capacity at const. P:    CP
 T  P
 H   S 
Divide Eq. 9 by dT :    T 
 T  P  T  P
 S  CP
→  
 T  P T
 S   V 
From Eq.16:      ….(19)
 P  T  T  P
Divide Eq. 9 by dP
 H   S   H   V 
   T  V →    V T  …..(20)
 P  T  P  T  P  T  T  P
Substitute the above partial derivatives in Eqs. 17 and 18
 V  
….(21)

dH = CP dT + V  T    dP
  T  P 
For homogeneous fluid of constant
composition
dT  V 
dS = C P   dP …..(22)
T  T  P
1  V 
Remember, for liquids     , substitute in Eq. (19) & (20)
V  T  P
 S 
→     V ….(23)
 P  T
 H 
and    (1   T )V ….(24)
 P  T
substitute Eqs. (23) & (24) in Eqs. (21) & (22)
→ dH = CP dT + V(1 – βT) dP ….(25)

For liquids.
dT
dS = C P  VdP ….(26)
T
Residual Properties:
MR = M - Mig
32
Where: MR is the residual property

M is the actual property
Mig is the ideal gas property
e.g. GR = G - Gig …..(27)
VR = V – Vig but V = ZRT/P and Vig = RT/P
RT
→ VR = ( Z  1) …..(28)
P
HR = H - Hig …..(29)
SR = S - Sig …..(30)
Note: Hig = H o  C Pmh (T  To ) ….(31)

ig ig
Sig = S o  C pms (T  To )
ig ig
…(32)
ig
Where: H o is the enthalpy of ideal gas at reference state conditions To and Po
S oig is the entropy of the ideal gas at reference state conditions To and Po
Substitute Eqs (31) & (32) in Eqs (29) & (30)
→ …….(33)
H = H o  C Pmh (T  To ) + HR
ig ig
S = S o  C pms (T  To ) + SR
ig ig ……(34)
The residual properties HR and SR can be found from the following equations:
HR (H R ) o ( H R )1
  ……(35)
RTC RTC RTC
SR (S R ) o ( S R )1
  …….(36)
R R R
(H R )o ( H R )1 ( S R ) o ( S R )1
The quantities , , and are plots versus Pr for various values of Tr in
RTC RTC R R
figures 6.6 to 6.13
Two phase systems:
33
Thermodynamic properties (V, H, S ..etc) are changed during a phase transition such as melting,
vaporization or sublimation except for Gibbs energy for a pure species does not change during a phase
transition.
i.e. Gα = Gβ
Where: Gα and Gβ are the molar Gibbs energies of the individual phases.
The vapor-pressure relation for the entire temperature range from the triple point to critical point is:
B
ln P sat  A 
T
Where: Psat is the vapor pressure
A and B are constants
Ex: Estimate V, U, H, and S for 1-butene vapor at 200oC and 70 bar if H and S are set equal to zero for
saturated liquid at 0oC. Assume that the only data:
TC = 419.6 K PC = 40.2 bar ω = 0.187 Tn = 267 K
C Pig
 1.967  31.63  10 3 T  9.837  10 6 T 2
R
Solution: V is calculated from PV = ZRT
Z = Zo + ωZ1
Zo and Z1 are found from Figs. 3.13 and 3.15 for
T 200  273 P 70
Tr   = 1.13 Pr   = 1.74
TC 419.6 PC 40.2
→ Zo = 0.476 , Z1 = 0.135
→ Z = 0.476 + 0.187(0.135) = 0.501
0.501(83.13)(473) cm 3
V = = 281.7
70 mol
H and S are calculated using the following path
(a) Vaporization at T1 & P1 = Psat Reference

state: B ΔH
P is estimated by the Eq. ln P
sat sat
 A
saturated
T ΔS Final state of
liquid ΔHlv
There are two points on the vapor-pressure curve arebutene at
butane at 473 K
known: normal boiling point; Psat = 1.013 bar, Tn=267
273 K K (a) ΔSlv & 70 bar
& critical point; PC = 40.2 bar, TC = 419.6 K & 1.273 bar

saturated
vapor
B butene at  H1R H 2R (d)
→ ln 1.013  A  …(1) 273 K
267
(b)
& 1.273 bar S 2R
R
 S1
34
Butene in ideal gas ΔHig ΔSig Butene in ideal gas
state at 273 K & state at 473 K &
(c) 70 bar
1.273 bar
B
And ln 40.2  A  ….(2)
419.6
From the two Eqs. above:
A = 10.134 & B = 2702.21

Substitute A & B in Psat Eq.
2701.21
→ ln P  10.143 
sat
273
→ Psat = 1.273 bar
0.38
H lv  1  Tr 
Heat of vaporization is found from the Eq.  
H nlv  1  Trn 
We need heat of vaporization at normal boiling point which is found in the Eq.
H nlv / Tn 1.092(ln PC  1.013)


R 0.93  Trn
Trn = Tn /TC = 267/419.6 = 0.636
H nlv / Tn 1.092(ln 40.2  1.013)

→  = 9.96
R 0.93  0.636
→ H n = 9.96(8.314)(267) = 22104 J/mol

lv
0.38
 0.349 
 H lv    (22104) = 21753 J/mol
 0.364 
And ΔSlv = ΔHlv/T =21753/273 = 79.64 J/mol.K
(b) Transition to the ideal gas state: since the pressure is low; the vapor 1-butene can
be assumed ideal, i.e. HR and SR → 0.
(c) Change from (T1 , P1) to (T2 , P2) in the ideal gas state.
ΔHig = C pmh (T2  T1 )

ig
ig
C Pmh C D
2
 T1T2 )  , A = 1.967, B = 31.63×10-3 , C = -9.837×10-6, D = 0
R 3 T1T2
C ig
→ pmh
= 12.367 → ΔHig = 12.367(8.314) (473 – 273) = 20564 J/mol
R
T2 P
S  C Pms
ig
ln  R ln 2
T1 P1
35
C igpms  D  ig
C Pms
 A  BTlm  TamTlm C   → = 12.145
R  (T1T2 ) 2  R
473 70
ΔSig = 12.145(8.314) ln  (8.314) ln = 22.16 J/mol.K
273 1.273
(d) Transition from ideal gas to the final actual state (T2 , P2) i.e. it must be estimate
H 2R and S 2R :
Tr = T2/TC = 473/419.6 = 1.13 Pr = P2/PC = 70/40.2 = 1.74
H 2R ( H 2R ) o ( H R )1
  2
RTC RTC RTC
o
( H 2R ) ( H 2R )1
From Fig. (6.7) = - 2.34 , and from Fig. (6.9) = - 0.62
RTC RTC
H 2R
→ = -2.34 + (0.187)(-0.62) = -2.46
RTC
→ H 2R  (8.314)(419.6)(-2.46) = -8582 J/mol
S 2R ( S 2R ) o ( S R )1
  2
R R R
( S 2R ) o ( S R )1
From fig. (6.11) = -1.63 and from fig. (6.13) 2 = -0.56
R R
S 2R
→ = -1.63 + (0.187)(-0.56) = -1.73
R
→ S 2R = (8.314)(-1.73) = -14.38 J/mol.K
The sum of the enthalpy and entropy change for the four steps give the total changes for the process:
H = ΔH = 21753 + 0 + 20564 – 8582 = 33735 J/mol
S = ΔS = 79.64 + 0 + 22.16 – 14.38 = 87.42 J/mol.K
The internal energy U is
U = H – PV = 33735 J/mol – 70 bar(105 N/bar)×281.7 cm3/mol (10-6 m3/cm3)
= 31763.1 J/mol
36
Thermodynamics of Flow Process
The application of thermodynamics to flow process is based on the law of mass

conservation, the linear momentum principle and the 1st and 2nd laws of
thermodynamics. Its application are to amount of fluid undergoing finite change in
state. e.g. the flow of gas through a pipeline.
Fundamental equations: Two idealizations are imposed from the start to

facilitate the application of thermodynamic principles to flow processes:
(1)Assume the flow is unidirectional at any cross section (entrance or exit).
(2)Assume the thermodynamics properties at any cross section do not vary in the
perpendicular to direction of flow.
Conservation of mass or continuity equation: The principle of conservation of
mass for a control volume shown in figure below:
W
dm
 1u1 A1   2 u 2 A2 = ∆ρuA …(1)
dt

Q
dm
: Rate of accumulation of mass within the control volume = Rate of change of total
dt
mass with time within the control volume
ρ: average fluid density
u: average fluid velocity
A: cross section area of entrance or exit duct
Control volume: an arbitrary volume enclosed by a boundary control surface, which is
equivalent to thermodynamic system.
At steady state the conditions within the control volume do not change with time, i.e.
dm
= 0 and the inflow of mass is exactly matched by the outflow of mass. Eq. (1)
dt
becomes:
 = constant = ρ2u2A2 = ρ1u1A1

m
 = mass flow rate = ρuA

m (kg/s, lb/s,….etc)
u 2 A2 u1 A1 uA
ρ = 1/V → m
 =   …….(2)
V2 V1 V
37
Conservation of Energy: The 1st law of thermodynamics was applied to closed system (nonflow
processes) and to a single stream steady state flow process to provide specific equation of energy
conservation. Here a more general equation applicable to an open system or to a control volume.
d (mU ) CV  1 
   Q  W s
  ( H  u 2  Zg )m
dt  2  fs ….(3)
Where: subscript "CV" = control volume, "fs" = flow system

d (mU ) CV
= Rate of accumulation of energy within the control volume, 
Q =heat flow
dt
rate, W =shaft work rate
m = dm/dt , Q  = dQ/dt ,W = dW/dt.
For most application ∆EP and ∆EK are negligible, multiply Eq.(3) by dt
d(mU)CV + ∆(Hdm)fs = dQ – dWs
Ex: A 1.5 m3 tank contains 500 kg of liquid water in equilibrium with pure water vapor
which fills the remainder of the tank. The temperature and pressure are 100 oC and
101.33 kPa. From a water line at a constant temperature of 70oC and a constant
pressure somewhat above 101.33 kPa, 750 kg is bled into the tank. If the temperature
and pressure in the tank are not to change as a result of the process, how much
energy as heat must be transferred to the tank?
Solution: The process is unsteady state , no ∆EP, and no ∆EK so the energy Eq. is
d(mU)tank + ∆(Hdm)fs = dQ – dWs
There is no shaft work, i.e. Ws = 0, integration the Eq.
→ m2U2 – m1U1 + (H2'm2' – H1'm1') = Q ..... (a) , the prime (') refer to flowing process.
[∆U = ∆H - ∆(PV)]tank , but the pressure and volume of the tank are not change, i.e. ∆(PV)tank = 0
 [∆U = ∆H]tank , the Eq. (a) becomes
Q = (m2H2 – m1H1)tank + (H2'm2' – H1'm1') …..(b) , no output from tank but input, i.e. H2'm2' = 0
From steam table; H 1' = 293 kJ/kg for saturated liquid at 70oC and 101.33 kP
Hltank = 419.1 kJ/kg , Hvtank = 2676 kJ/kg at 100oC and 101.33 kPa
Volume of vapor in the tank initially: V1v =1.5-500×0.00104=0.98 m3 (0.00104=specific volume of liquid at
100oC)
Mass of vapor in the tank initially: m1v = 0.98/1.673 = 0.772 kg (1.673 = specific volume of vapor at 100oC)
 (m1H1)tank = m1l H 1l + m1v H 1v = 500(419.1) + 0.772(2676) = 211616 kJ

38
m2 = 500 + 0.772 + 750 = 1250.772 = m2v + m2l ……(c)

1.5 = 1.67 m 2v + 0.00104 m 2l ....…(d)
So, from Eqns. (c) & (d) → m2l = 1250.65 kg & m2v = 0.116 kg
Since the conditions in the tank are the same in two cases, i.e. H 2l = H 1l & H 2v = H 1v
 (m2H2)tank = m2l H 2l + m2v H 2v = 1250.65(419.1) + 0.116(2676) = 524458 kJ
Substitute m2H2 & m1H1 in Eq. (b) → Q = 524458 - 211616 – 750(293) = 93092 kJ
Energy equation for steady state process:
d (mU ) CV
At steady state the term = 0 in Eq. (3)
dt
 1 
→ Eq.(3) becomes    Q  W s …..(4)
 ( H  u 2  Zg ) m
 2  fs
For one entrance and one exit in the control volume m out  m in , divided Eq. (4) by m

u 2
→ H   g Z  Q  W S ……(5) per unit mass of fluid
2
Mechanical Energy Balance and Bernoulli Equation:
dH = TdS + VdP
For a reversible process TdS = dQ
→ dH = dQ + VdP
P2
Integration → H  Q   VdP …..(6)

P1
u 2
From Eq. (5) H  Q  WS   gZ Substitute in Eq. (6)
2
P2
u 2
→ -WS =
P1
 VdP 
2
 gZ
Because the viscous nature of real fluids induced fluid friction, so the friction term F is added to the last Eq.
P2
u 2
-WS =  VdP   gZ + F …..(7) Mechanical energy balance equation
P1
2
For non viscous fluid, F = 0 and for incompressible fluid (i.e. V does not change with pressure) which does
not exchange the shaft work with the surrounding (i.e. WS = 0)
P2
P
 VdP  VP 
P1

Substitute in Eq. (7)
39
P u 2
→   gZ  0 ……(8) (Bernoulli Eq.)
 2
Ex:
Solution: Steady flow, no work, no heat transfer, so Bernoulli Eq. can applied
P u 2
  gZ  0 ……….(*)
 2
From steam table at 20oC, specific liquid volume
V1 = V2 = V = 0.001002 m3/kg → ρ = 998 kg/m3
 /
m 2000 / 998
P1 = 150 kPa, P2 = ? u1 = =  2 = 10.206 m/s
A 4 (0.5)
2000 / 998
u2 = = 20.83 m/s , ∆Z =Z2 – Z1 = 0 - 15 = - 15 m substitute in Eq. (*)
 / 4(0.35) 2
P2  150  10 3 (20.83) 2  (10.206) 2
→   9.81( 15)  0 → P2 = 132.2 kPa
998 2
Flow in Pipes: The steady state flow of fluid in a straight length of pipe is the pressure change
accompanying flow.
The maximum velocity of fluid in pipes can be attainable as follows: consider a gas in steady state
adiabatic flow in a horizontal pipe of constant cross section area:
u 2
Eq. (5) becomes: H  = 0 , in differential form dH = -udu …..(9) Since m is constant, Eq. (2)
2
 uA 
can be written in differential form d  = 0
V 
u du udV udV
Since A is constant → d   = 0 , whence:  2 = 0 → du = substitute in Eq.(9)
V
  V V V
u 2 dV
→ dH = -
V
u 2 dV
But TdS = dH – VdP → TdS = - - VdP
V
2
u max dV
Maximum velocity is reached at reversible adiabatic flow (i.e. isentropic); dS = 0 → + VdP = 0
V
40
 P 
Or
2
u max  V 2   This is equivalent to the speed of sound, i.e. the maximum velocity of fluid
 V  S
in pipes is equal to the speed of sound. The velocity of fluid can be higher than speed of sound in the
converging/diverging nozzles.
Expansion Process: It is a flow process accompanying to the sharp reduction in pressure. Such as flow
through nozzles, turbines or expanders, and throttling devises such as orifices and valves.
Nozzle: It is a device that causes the interchange of internal and kinetic energy of fluid (U → u) as a result
of changing of cross-section area available of flow.
Since WS = 0, Q = 0 and ∆EP = 0, the energy Eq. for the nozzle is
dH = -udu Integrating for any two sections in nozzle
1
→ H2 – H1 = ( u 2  u 22 )
2 1
For subsonic flow in a converging nozzle, the velocity increases and pressure decreases as the cross-
sectional area diminishes. In a diverging nozzle with supersonic flow, the area increases, but still the velocity
increases and the pressure decreases.
In the converging nozzle the maximum velocity is at the throat with isentropic condition and when the
pressure is low enough at the throat that the critical value P2/P1 is reached (e.g. for steam the critical value
P2/P1 is 0.55)
 P 
2
u throat  V 2  
 V  S
The ratio pressure for ideal gas between the entrance

and the throat is
 /( 1)
P2  2 
  [Ideal gas]
P1    1 
For ideal gas with constant CP and isentropic expansion in nozzle the relation between u & P is
2P1V1   P2 
(  1) / 

u u 
2 2
1    
  1   P1
2 1
  
Mach number (M): It is the ratio between the actual velocity and the sonic velocity, if M < 1 (subsonic), M >
1 (supersonic), and M = 1 (sonic)
41
Ex: A high velocity nozzle is designed to operate with steam at 700 kPa and 300oC. At the nozzle inlet the
velocity is 30 m/s. Calculate the ratio of A2/A1. Assume the nozzle operate isentropically, where the pressure
at the throat is 600 kPa.
u1 A1 u 2 A2 A2 u1V2
Solution:  → 
V1 V2 A1 u 2V1
u1 = 30 m/s, and from steam table at 700 kPa and 300oC, V1 =371.39 cm3/g, H1 =3059.8 kJ/kg, S1 =7.3
kJ
kg .K
u 22 = u12 - 2(H2– H1)
kJ
For isentropic expansion, S2 = S1 = 7.3 kg .K , and P2 = 600 kPa → H2 = 3020.4 kJ/kg, V2 = 418.25 cm3/g
 u2 = (30)2 – 2(3020.4×103 - 3059.8×103) = 79693.29 m2/s2 → u 22 = 282.3 m/s
A2 30  418.25
 = 0.12
A1 282.3  371.39
Turbine or Expander: It consists of set of alternate of nozzles and rotating blades through which gas flows in
a steady state expansion process whose overall effect is the efficient conversion of the internal energy of a
high-pressure stream into work.
In the turbine or expander, the ∆EP is very little so it is negligible, the difference in the fluid velocities in
the inlet and outlet pipes is very low (∆EK = 0), and if no heat transfer (Q = 0) the energy equation becomes:
W  m
 H or Ws = -∆H …….(10)
s
The maximum work in the turbine is at reversible and adiabatic condition (isentropic)
Ws
Ws (isentropic) = -∆HS ……(11)
42
Ws (actual )
The efficiency of turbine is   or according to Eq. (10) & (11)
Ws (isentropic )
H

H S
Where ∆H is the actual and ∆HS is at isentropic condition. 1
The relation between the H & S are shown in the adjacentHfigure.

P ∆H ∆HS
1
Note: For any thermodynamics property (M) 2

2/
M = xlMl+ xvMv = (1-xv) Ml + xvMv = Ml + xv(Mv – Ml) P2 ∆S
l v v l v
e.g. H = H + x (H - H ) ; x : mole fraction of vapor
Ex: A steam turbine with rated capacity of 56000 kW operates with steam at inlet conditions of 8600 kPa and
500oC and discharges into a condenser at a pressure of 10 kPa. Assuming a turbine efficiency
S of 75%
determine the state of the steam at discharge and a mass rate of flow of the steam.
Solution: From steam table at P1 = 8600 kPa, T1 = 500oC (superheated steam)

H1 = 3391.6 kJ/kg, S1 = 6.686 kJ/kg.K
Assume the expansion to P2 = 10 kPa is isentropic, S 2' = S1 = 6.686 kJ/kg.K

So from steam table, S for saturated steam > S 2' (i.e. the steam is wet) Ws
 S 2' = Sl + xv(Sv – Sl)
From steam table at 10 kPa, Sv = 8.1511, Sl = 0.65 kJ/kg.K
 S 2' = 6.686 = 0.65 + xv(8.1511 - 0.65) → x2' = 0.805
H 2' = Hl + x2' (Hv – Hl) = 191.8 + 0.805(2584.8 - 191.8) = 2117.4 kJ/kg
Where Hl and Hv are extracted from steam table at 10 kPa
∆HS = H 2' - H1 = 2117.4 - 3391.6 = - 1274.2 kJ/kg
H
 → ∆H =  ∆HS = 0.75 (-1274.2) = - 955.6 kJ/kg
H S
v
H2 = H1 + ∆H = 3391.6 - 955.6 = 2436 kJ/kg < H saturated (i.e. the actual final state of steam is also wet)
2436 = 191.8 + xv(2584.8 - 191.8) → x2 = 0.938
S2 = 0.65 + 0.938(8.1511 - 0.65) = 7.687 kJ/kg.K
The steam rate is found from W s   m

 H
W s 56000
→ m  = = 59.02 kg/s
 ( H 2  H1 )  ( 2436  3391.6)
43
Ex: A stream of ethylene gas at 300oC and 45 bar is expanded adiabatically in a turbine to 2 bar. Calculate
the isentropic work produced. Determine the properties of ethylene by (1) Ideal gas equation (2) appropriate
generalized correlation.
Solution: Ws = -∆Hs …..(a)

ig
(1) Ideal gas: ∆H = C Pmh (T2 – T1)
T2 P
ig
For isentropic case: ∆S = 0 = C Pms ln  R ln 2 , P1 = 45 bar, P2 = 2 bar, T1 = 300oC = 573 K
T1 P1
T2 2
ig
C Pms ln  R ln → C Pms ig
/R (ln T2 - ln 573) = - 3.114
573 45
  3.114 
→ T2 = exp  ig  6.35  ….(b)
 C Pms / R 
ig T1  T2 T1  T2
C Pms /R = A + BTlm + CTamTlm ……(c) Tam = , Tlm =
2 ln T1 / T2
Where: A = 1.424, B = 14.394×10-3, C = - 4.392×10-6
By iteration between Eqs. (b) & (c) for T2  T1
→ T2 = 370.8 K
C
ig
C Pmh /R = A + BTam + 2
( 4Tam  T1T2 ) = 7.224 → C Pmh
ig
= 7.224×8.314 = 60.1
3
 ∆H = 60.1(370.8 – 573) = - 12154 J/mol
→ From Eq. (a) Ws = - (-12154) = 12154 J/mol
(T2 – T1) + H 2R  H1R

ig
(2) Ethylene as actual gas: ∆H = C Pmh , H 2R = 0 [P2 = 2 bar ; i.e. ideal]
From Appendix B: TC = 282.4 K, PC = 50.4 bar,  = 0.085
T1 P
At initial state: Tr1 = = 573/282.4 = 2.032 , Pr1 = P = 45/50.4 = 0.893
TC C
( H 1R ) o ( H 1R )1
From Fig. (6.6) = -2.35 and from Fig. (6.8) = 0.01
RTC RTC
( H 1R ) ( H 1R ) o ( H 1R )1
= +  = - 2.35 + 0.085(0.01) = - 2.348
RTC RTC RTC
→ H 1R = - 553 J/mol
T2 P
ig
T2 can be found from the equation: ∆S = 0 = C Pms ln  R ln 2 + S 2R - S1R , S 2R = 0 (P2 = 2 bar)
T1 P1
44
( S1R ) o ( S1R )1
From Fig. (6.10), = - 0.09, and from Fig. (6.12), = - 0.025
R R
( S1R ) (S R )o ( S1R )1
= 1 +  = - 0.0902 → S1R = -0.0902×8.314 = - 0.75 J/mol.K
R R R
T2 2
 ∆S = 0 = C Pms
ig
ln  8.314 ln  (0.75)
573 45
  26.56 
→ C pms ln T2/573 = -26.56 → T2 = exp    6.35 …….(d)
ig
C ig 
 pms 
Also by iteration between Ens. (d) & (c) → T2 = 365.8 K
ig ig
∆HS = C pmh (T2 – T1) - H 1R , C pmh = 60 J/mol.K
→ ∆HS = 60(365.8 – 573) – (- 553) = -11879 J/mol
 Ws(isentropic) = -∆HS = 11879 J/mol
Throttling Process: It is a process where the fluid flows through a restriction, such as an orifice, partly
open valve, porous plug and capillary tubes result in pressure drop without any appreciable change in
kinetic energy.
In throttling process there is no shaft work, (Ws = 0, differs of turbine), no heat transfer (Q = 0), no change
in elevation (∆EP = 0), and (∆EK = 0), so the energy Eq. is
∆H = 0 or H2 = H1 but H = U + PV
→ U1 + P1V1 = U2 + P2V2
For ideal gas ∆H depends on temperature, i.e. there is no
change in temperature. For most real gases a reduction in Partly open valve
pressure at constant enthalpy result in a decrease in temperature.
If a saturated liquid is throttled to a lower pressure, some of
liquid vaporizes. If a wet vapor is throttled to a sufficiently low Porous plug
low pressure the liquid is vaporize and the vapor becomes superheated.
Ex: Propane gas at 20 bar and 400 K is throttled in a steady state flow process to 1 bar. Estimate the final
temperature and its entropy change.
ig
Solution: for throttling process: ∆H = 0 = ∆H = C pmh (T2 – T1) + H 2R - H 1R , [P2 = 1 bar; H 2R = 0]
H1R
→ T2 = ig +T1 …..(a)
C Pmh
From Appendix B; TC = 369.8 K, PC = 42.5 bar ,  = 0.152
Tr1 = T1/TC = 400/369.8 = 1.082, Pr1 = P1/PC = 20/42.5 = 0.471
45
o 1
 HR   H 1R 
From Fig. (6.6)  1  = - 0.425, and from Fig. (6.8)   = - 0.167
 RTC   RTC 
o 1
 R   H 1R   H 1R 
  H1  =   +    = - 0.425 + 0.152(- 0.167) = - 0.4504 J/mol
 RTC   RTC   RTC 
→ H 1R = 8.314×369.8×(-0.4504) = - 1384.77 J/mol

C
ig
C Pmh /R = A + BTam + 2
( 4Tam  T1T2 ) …..(b) , from table (4.1), A=1.213, B=28.875×10-3, C=
3
-8.824×10-6
By iteration between Eqs. (a) and (b) for T2  T1 → T2 = 385 K
ig ig
C Pmh /R = 11.155 → C Pmh = 92.734 J/mol
T2 P
The entropy change is ∆S = C Pms ln
ig
 R ln 2 - S1R
T1 P1
ig ig
Because the difference in temperature is very little, it can be assume C Pms = C Pmh = 92.734
( S1R ) (S R )o ( S R )1 (S R )o ( S R )1
= 1 + 1 from Fig. (6.10) 1 = - 0.24 and from Fig. (6.12) 1 = -0.24
R R R R R
( S1R )
= -0.24 + 0.152(-0.24) = -0.288 S1R = -2.4 J/mol.K
R
 ∆S = 92.743ln 385
400
 8.314 ln
1
20
 ( 2.4) = 23.76 J/mol.K
Compression Process: It is a flow process result in increasing in pressure such as happened in

compressor, pump, fans, blowers and vacuum pump devices
Compressor: It is a device where the compression of gases is accomplished. It may consists of rotating
blades (like a turbine operating in reverse) which used for high volume flow and discharge pressure is not to
high or consists of cylinders with reciprocating pistons when high pressure is required.
The Eq. of energy is the same to that of turbine or expander;
i.e. ∆EP = 0, ∆EK = 0 and if Q = 0

2
→W =- m
 ∆H or Ws = - ∆H
s
Ws (isentropic ) 2/
The compressor efficiency:  
Ws ( actual ) ∆H
H P2 ∆HS
H S
Or 
H
1
P1 ∆S
2
W s compressor S
46
1
Ex: Air at 100 kPa and 280 K is compressed steadily to 600 kPa and 400 K. The mass flow rate of the air is
0.02 kg/s, and a heat loss of 16 kJ/kg occurs during the process. Assuming the changes in kinetic and
potential energies are negligible, determine the necessary power input to the compressor. TC = 132.45 K,
PC =37.74 bar,  = 0.
Solution: It is a steady flow process, so the energy Eq. is
∆H + 1/2u2 + g∆Z = Q - Ws but 1/2u2 = 0, g∆Z = 0
→ ∆H = Q - Ws or  W
 ∆H = Q
m 
s
∆H = C pmh (T2  T1 )  H 2R  H 1R
ig
[ H 1R = 0 ; P1 = 100 kPa]
ig
C Pmh / R  A  BTam  C / 3( 4Tam
2
 T1T2 )  D / T1T2 A = 3.355, B = 0.575×10-3, D = -0.016×105
Tam = (T1+T2)/2 = (280+400)/2 = 340 K

ig ig
→ C Pmh / R = 3.54 → C Pmh = 3.54×8.314 = 29.43 kJ/kmol
o
 H 2R   H 2R 
H R
2 is found by   =   Tr2 = T2/TC = 400/132.45 = 3.02, Pr2 = P2/PC = 6/37.74 = 0.16
 RTC   RTC 
o
 HR 
From Fig. (6.6)  2  = - 0.05 → H 2R = - 0.05×8.314×132.45 = - 55.06 kJ/kmol
 RTC 
 ∆H = 29.43 (400 – 280) + (-55.06) = 6419.54 kJ/kmol, but there is 0.02 kg/s of air
or 0.02×29 = 0.58 kmol/s → m
 ∆H = 6419.54×0.58 = 3723.33 kJ/s

Q = - 16×0.02 = - 0.32 kJ/s
 W s
= 
Q - m
 ∆H = - 0.32 - 3723.33 = - 3723.65 kJ/s
Ex: Saturated vapor steam at 100 kPa (tsat = 99.63oC) is compressed adiabatically to 300 kPa. If the
compressor efficiency is 75%, what is the work required and what are the properties of the discharge stream?
Solution: Ws = - ∆H = -(H2 – H1) ....(a)
From steam table for saturated vapor at 100 kPa: H1 = 2675.4 kJ/kg, S1 = 7.36 kJ/kg.K
For isentropic compression, S2 = S1 = 7.36 kJ/kg.K and at 300 kPa,
47
From steam table (superheated steam) H 2' = 2888.8 kJ/kg.K

 ∆HS = H 2' - H1 = 2888.8 – 2675.4 = 213.4 kJ/kg
H S 213.4
→ ∆H = = = 284.53 kJ/kg
 0.75
 from Eq. (a) Ws = - 284.53 kJ/kg
H2 = ∆H + H1 = 284.53 + 2675.4 = 2960 kJ/kg

From steam table, at H2 = 2960 and 300 kPa,
S2 = 7.5 kJ/kg.K and T2 = 246.1oC
Pump: It is rotating equipment used to move the liquids from one location to another.
The same equation as for compressor is used. i.e. if adiabatic pump is used:
Ws = - ∆H
But dH = TdS + VdP
For isentropic process, dS = 0, and dH = VdP
P2
→ Ws(isentropic) = - ∆HS = -  VdP but for liquids V is independent of P

P1
→ Ws(isentropic) = - ∆HS = -V(P2 – P1)
Also another useful equations for liquids:
∆H = CP∆T + V (1 – βT) ∆P
T2
ln
∆S = CP T1 - β V∆P
Ex: Water at 45oC and 10 kPa enters an adiabatic pump and is discharged at a pressure of 8600 kPa. Assume
the pump efficiency to be 75%. Calculate the work of the pump, the temperature change of the water, and the
entropy change of the water.
Solution: From steam table for saturated liquid at 45oC and 10 kPa: V = 1010 cm3/kg
Also β = 425×10-6 K-1 , CP = 4.18 kJ/kg.K
Ws(isentropic) = - ∆HS = -V(P2 – P1) = -1.01×10-3(8600 – 10) = - 8.676 kJ/kg
H S 8.676
∆H = = = 11.57 kJ/kg → Ws = - ∆H = - 11.57 kJ/kg
 0.75
∆H = CP∆T + V (1 – βT) ∆P = 11.57 = 4.18∆T + 1.01×10-3(1 - 425×10-6×318.15)(8600 – 10)
→ ∆T = 0.97 K or 0.97oC = T2 – T1 → T2 = 319.12 K

48
T2
ln
∆S = CP T1 - β V∆P = 4.18 ln(319.12/318.15) - 425×10-6×1.01×10-3(8600 – 10) = 0.009 kJ/kg.K
Ejector: It is a vacuum pump used to remove the gases from an
evacuated space and compress them for discharge at a high pressure.
Steam Power Plant
In a conventional power plant the molecular energy of fuel is released by a combustion of process.
The function of the work producing device is to convert part of the heat of combustion into mechanical
energy.
Simple steam power plant: The figure below shows a simple steady state flow process in which steam
generated in a boiler is expanded in an adiabatic turbine to produce work. The discharge stream from the
turbine passes to a condenser from which it is pumped adiabatically back to the boiler.
Q H
TH 1 2 Boiler 2
1
Turbine
(turbine)
TC 3
4 (pump) 3
4
Condenser
Carnot cycle on TS diagram

Q C
The steps of the process cycle are:
Step 1 – 2: Isothermal absorption of heat at TH and at constant pressure and produces saturated vapor
steam. (vaporization process)
Step 2 – 3: Reversible adiabatic (isentropic) expansion of saturated vapor to a pressure at which Tsat = TC.
Step 3 – 4: Isothermal rejection of heat at TC. (condensation process)
Step 4 – 1: The cycle back to its origin producing saturated liquid water. It is isentropic compression process.
The thermal efficiency of this cycle is the same of the Carnot engine:
W T
  1 C
QH TH
49
Rankine cycle: It is an alternative model cycle of Carnot cycle for steam power plant. The steps of
Rankine cycle are:
1 – 2: A constant pressure (isobar) heating process in a boiler, where the liquid water is heated to its boiling
point, vaporization, and superheating the vapor.
2 – 3: Reversible adiabatic (isentropic) expansion of vapor in the turbine to a pressure of the condenser and
producing a wet exhaust.
3 – 4: A constant pressure, constant temperature process in a condenser to produce saturated liquid at point 4.
4 – 1: Reversible adiabatic (isentropic) pumping of the condensed liquid to the pressure of the boiler.
The simple practical power plant is differ from Rankine cycle by the reversible steps becomes irreversible;
i.e. steps (2 – 3) and (4 – 1).
2 2
1 1
4 3 4
3' 3
Simple practical power plant

Rankine cycle
The energy equation of the boiler and condenser: 

Q = m
 H or Q = ∆H
Ex: Steam generated in a power plant at a pressure of 8600 kPa and a temperature of 500oC is fed to a
turbine. Exhaust from the turbine enters a condenser at 10 kPa where it is condensed to saturated liquid
which 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 75%.
(c) If the rating of the power cycle of part (b) is 80000 kW, what is the steam rate and what are the heat
transfer rates in the boiler and condenser?
Solution: (a) From steam table at P2 = 8600 kPa, T2 = 500oC (superheated steam)
H2 = 3391.6 kJ/kg, S2 = 6.686 kJ/kg.K
50
'
Assume the expansion to P3 = 10 kPa is isentropic, S 3 = S2 = 6.686 kJ/kg.K
So from steam table, S for saturated steam > S 3' (i.e. the steam is wet)
 S 3' = Sl + xv(Sv – Sl)
From steam table at 10 kPa, Sv = 8.1511, Sl = 0.65 kJ/kg.K
 S 3' = 6.686 = 0.65 + xv(8.1511 - 0.65) → x3' = 0.805
H 3' = Hl + x3' (Hv – Hl) = 191.8 + 0.805(2584.8 - 191.8) QH

= 2117.4 kJ/kg
1
l v
2
Where H and H are extracted from steam table at 10 kPa
'
∆HS = H 3 - H2 = 2117.4 - 3391.6 = - 1274.2 kJ/kg
 Ws (isentropic) = - ∆HS = 1274.2 kJ/kg

4 3
The enthalpy of saturated liquid at 10 kPa
QC
sat o
(T = TC = 45.8 C) H4 = 191.8 kJ/kg
Q(condenser) = H4 – H 3' = 191.8 – 2117.4 = - 1925.6 kJ/kg
For the pump: from steam table for saturated liquid at 45.8oC and 10 kPa: V = 1010 cm3/kg
Ws(isentropic) = - ∆HS = -V(P1 – P4) = -1.01×10-3(8600 – 10) = - 8.7 kJ/kg
H1 = H4 + ∆HS = 191.8 + 8.7 = 200.5 kJ/kg
Q(boiler) = H2 – H1 = 3391.6 – 200.5 = 3191.1 kJ/kg
The net work of the Rankine cycle is the sum of the work of the turbine and the pump, [i.e. the difference the
absolute values]
Ws(Rankine) = 1274.2 – 8.7 = 1265.5 kJ/kg
Or the net work is the sum of Q(boiler) and Q(condenser), [i.e. the difference the absolute values]
Ws(Rankine) = 3191.1- 1925.6 = 1265.5 kJ/kg
The thermal efficiency of the Rankine cycle is
Ws ( Rankine) 1265.5
 = = 0.3966 or 39.66%
Q (boiler ) 3191.1
(b) If the turbine efficiency 75%
51
→ Ws(turbine) = Ws (isentropic)× = 1274.2×0.75 = 995.6 kJ/kg = - ∆H
H3 = H2 + ∆H = 3391.6 – 995.6 = 2436 kJ/kg
Q(condenser) = H4 – H3 = 191.8 – 2436 = - 2244.2
For pump:
Ws(isentropic) = - 8.676 kJ/kg
Ws (isentropic )
Ws(pump) = = -8.676/0.75 = -11.57 kJ/kg = - ∆H = - (H1 – H4)

 H1 = H4 + ∆H = 191.8 + 11.57 = 203.4 kJ/kg
Q(boiler) = H2 – H1 = 3391.6 – 203.4 = 3188.2 kJ/kg
Ws (net ) 955.6  11 .6
The thermal efficiency of the entire cycle is   = = 0.2961
Q (boiler ) 3188.2
(c) For the power rating 80000 kW, the steam rate is calculated as:
W ( net )  m
 Ws ( net )
s
W s ( net ) 80000
 
→ m = = 84.75 kg/s
Ws ( net ) 944

Q = m
 H
 Q (boiler) = 3188.2×84.75 = 270.2×103 kJ/s

 (condenser)
Q = - 2244.2×84.75 = -190.2×103 kJ/s
Note:  (boiler )  Q
Q  (condenser)
= W s (net )
52
Refrigeration
The word of refrigeration implies the maintenance of a temperature below that of the surrounding by
absorption of heat at a low temperature by evaporation of a liquid in a steady state flow process and returned
the vapor to its liquid state by either compressed and condensed it or it absorbed by a liquid of low volatility
which evaporated at high pressure.
Refrigeration used in the air conditioning, preservation of food and beverages and in the manufacture of
ice and dehydration of gases.
Carnot Refrigerator: Basically, a refrigeration cycle is a reversed heat engine, where the heat is absorbed
at a low temperature and rejected to the surrounding at a high temperature. This is cannot be accomplished
according to the 2nd low of thermodynamic without use of external energy. Carnot (ideal) refrigerator like the
ideal heat engine consists of two isothermal steps where QC is absorbed at low temperature TC and QH
rejected at high temperature and two adiabatic steps.
The measure of performance of a refrigerator is called the coefficient of performance (COP) ω, defined by:
heat absorbed at lower temperature Desired output

 = required input
net work
Q
→  W
C
…….(1)
Where: W  QH  QC …….(2)
Divided Eq. (2) by QC
W QH QH TH
→  1 but for Carnot cycle 
QC QC QC TC
W TH T  TC
 QC

TC
1= H
TC
Compare with Eq. (1)
TC
 [This is only for Carnot Cycle]
TH  TC
The vapor-compression cycle: A liquid evaporated at constant pressure provides a means for heat
absorption at constant temperature. Likewise, condensation of the vapor after compression to a high pressure,
provides for the rejection of heat at constant temperature. The liquid from the condenser is returned to its
original state by an expansion process. When compression and expansion processes are isentropic equivalent
53
to Carnot cycle as shown in figure (1) except that superheated vapor from the compressor (point 3) must be
cooled to its saturation temperature before condensation begins.
3 QH
4 4 3
2 Expander
1
1
2
QC
Figure (1)
The heat absorbed in the evaporator QC is
QC = ∆H = H2 – H1
The heat rejected in the condenser QH is
QH = ∆H = H4 – H3
According to Eq. (2) = (H3 – H4) – (H2 – H1)

W
H 2  H1
According to Eq. (1)  
( H 3  H 4 )  ( H 2  H1 )
The process requires turbine or expander that operate on two phase liquid/vapor mixture and this is
impractical for small units. In the small units such as refrigerators and air conditioners the expansion process
is accomplished by throttling the liquid from the condenser through a partly opened valve (for simplicity and
lower cost) as shown in figure (2). The path 4 → 1 represent constant enthalpy and path 2 → 3' represent
isentropic compression:
H 2  H1
 
H3  H2
The rate of circulation of refrigerant is
Q C
 
m
H 2  H1
Tons of refrigeration: It is heat absorption at the rate of 12000 Btu/hr or 12660 kJ/hr. This corresponds
approximately to the rate of heat removal required to freeze 1 ton of water initially at 32oF (0oC).
54
QH
4 3
1
2
3' 3 QC
Figure (2)
4
Ex: A refrigerated space is maintained at 10oF and cooling water is available at 70oF. The evaporator and
condenser are of sufficient size that a 10oF minimum-temperature difference for the heat transfer can be
2 capacity is 120000 Btu/hr and the refrigerant is Freon-12.
released in each. The refrigeration
1
(a) What is the value of ω for a Carnot refrigerator?
(b) Calculate ω and m  for the vapor compression cycle with expander (Fig. 1).
(c) Calculate ω and m  for the vapor compression cycle with valve (Fig. 2) if the compressor efficiency
is 80%.
TC
Solution: (a) For Carnot refrigerator:  
TH  TC
TC = 10 – 10 = 0oF = 0 + 460 = 460 R
TH = 70 + 10 = 80oF = 80 + 460 = 540 R
460
→  = 5.75
540  460
That is, 5.75 kJ of heat is removed from the refrigerated space for each kJ of work supplied.
Notice that the value of ω can be greater than unity. That is, the amount of heat removed from the
refrigerated space can be greater than the amount of work input.
(b) Freon-12 as a refrigerant, its enthalpies for states 1, 2, 3, and 4 can be read form table (9.1) and figure
(9.3).
At 0oF in the table (9.1) Freon-12 evaporates at pressure P1 = P2 = 23.85 Psia and its properties are:
H2 = 77.27 Btu/lbm and S2 = 0.169 Btu/lbm.R

55
At 80oF Freon-12 condensed at pressure P4 = P3 = 98.87 Psia and its properties are:
H4 = 26.37 Btu/lbm and S4 = 0.055 Btu/lbm.R
Since S3 = S2 = 0.169 Btu/lbm.R, from Fig. (9.3) at P3 = 98.87 Psia
H3 = 88.3 Btu/lbm
According to Fig. (1), the state (1) is a two-phase mixture, so:
S1 = Sl + xv(Sv – Sl)
Since S1 = S4 = 0.055 Btu/lbm.R, Sv = 0.169 Btu/lbm.R and Sl = 0.0193
→ 0.055 = 0.0193 + xv(0.169 - 0.0193)
xv = 0.237
Similarly H1 = Hl + xv(Hv – Hl) ; Hv = 77.27 Btu/lbm , Hl = 8.52 Btu/lbm (at P = 23.85 Psia)
→ H1 = 8.52 + 0.237(77.27 – 8.52) = 24.83 Btu/lbm
H 2  H1 77.27  24.83
The coefficient of performance is  =
( H 3  H 4 )  ( H 2  H1 ) (88.3  26.37)  (77.27  24.83)
= 5.53
QC 120000
The Freon-12 circulation rate is: m  = = 2288 lbm/hr
H 2  H1 77.27  26.37
(c) For the cycle with valve, the expansion step occurs in throttling process, i.e.
H1 = H4 = 26.37 Btu/lbm
For the compression step: ∆HS = (H3 – H2)S = 88.3 – 77.27 = 11.03 Btu/lbm
H S 11 .03
H  = = 13.8 Btu/lbm
 0.8
H 2  H 1 77.27  26.37
 = = 3.69
H3  H2 13.8
QC 120000
Circulation rate is m  = = 2358 lbm/hr
H 2  H1 77.27  26.37
56
Choice of Refrigerant: The coefficient of refrigerator of a Carnot refrigerator is independent of

refrigerant. But for irreversible vapor-compression cycle cause the coefficient of performance of practical
refrigerators to depend to some extent on the refrigerant. Such characteristic are:
1- Non toxic.
2- Non flammable.
3- Cheap in cost.
4- Non corrosive.
5- The vapor pressure of the refrigerant should be greater than atmospheric pressure.
Ammonia(R-717), methyl chloride(R-40), carbon diaoxide(R-744), propane(R-290), Freon-12

(dichlorodifluoromethane; R-12) and other hydrocarbons and various halogenated hydrocarbons are used as
refrigerant.
Heat Pump: A reversed heat engine, is a device for heating houses and commercial buildings during the
winter and cooling them during the summer. In the winter it operates so as to absorb heat from the
surroundings and reject heat into the building. The objective of a heat pump, however, is to
maintain a heated space at a high temperature.
A heat pump is used to meet the heating requirements of a house and

Ex: TC
maintain it at 20°C. On a day when the outdoor air temperature drops
to -2°C, the house is estimated to lose heat at a rate of 80,000 kJ/h. If
the heat pump under these conditions has a ωHP of 2.5, determine (a)
the power consumed by the heat pump and (b) the rate at which heat
is absorbed from the cold outdoor air.
Desired output 
Q
Solution: (a) ωHP = required input = H
W
If the house is to be maintained at a constant temperature of 20°C,
QC
the heat pump must deliver heat to the house at the same rate, 80000 kJ/hr
Q H 80000
→ W   = = 32000 kJ/hr QC
HP 2.5
(b)
 = Q
Q   W = 80000 – 32000 = 48000 kJ/hr
C H
57
Liquefaction processes: Liquefied gases are common for a variety of purposes. For example the
separation of oxygen and nitrogen from air, preparation of liquid propellants for rockets, liquid propane in
cylinders is used for a domestic fuel, and natural gas is liquefied for ocean transport.
Liquefaction results when a gas is cooled to a temperature in the two phase region. This may be
accomplished in several ways:
1. By heat exchange at constant pressure.

2. By expansion in a turbine from which work is obtained.
3. By a throttling process.
The three methods are illustrated in the adjacent

figure. For case (3) the change of state from A to
A' is most easily accomplished by compression of
the gas to the final pressure at B, followed by
constant pressure cooling to A' then isentropic B
expansion by path (3'). So the temperature must be
low enough and the pressure high enough prior
the throttling that the constant enthalpy path cuts A'
A
into the two-phase region.
The simplest kind of liquefaction system known 1

as the Linde-Hampson system is shown in 2 3
liquid-gas 3'
figure below. After compression, the gas region
is precooled to ambient temperature.
The lower the temperature of the gas
entering the throttle valve, the fraction
of gas that is liquefied. under the
steady state conditions an energy
balance around separator, valve and
Heat-exchanger
cooler gives:Or precooler
(m
 H ) fs = 0 , or
H4 = H7z + H9(1-z) (per unit mass of fluid)
Where z is fraction of gas that is liquefied
Cooler
Ex: Natural gas is assumed to be here pure methane
Throttle
is liquefied in a simple Linde-Hampson system. valve
Compression is to 60 bar and precooling is to
300 K. The separator is maintained at a pressure
of 1 bar, and unliquefied gas at this leaves the
cooler at 295 K. What fraction of the gas is
liquefied in the system and what is the temperature
of the high pressure gas entering the throttle valve?
58
Solution: From Perry's chemical engineering handbook, for superheated methane:
H4 = 1140 kJ/kg (at 300 K and 60 bar)

H9 = 1188.9 kJ/kg ( at 295 K and 1 bar)
For saturated conditions at 1 bar, Tsat = 111.45 K
H7 = 285.4 kJ/kg (for saturated liquid)

H8 = 796.9 kJ/kg (for saturated vapor)
To find fraction of liquefied gas:
H9  H4 1188 .9  1140
H4 = H7z + H9(1-z) → z = = 0.0541
H9  H7 1188 .9  285.4
Energy balance around the cooler:
1(H5 – H4) + (1 – z)(H9 – H8) = 0
→ H5 = 1140 – 0.9459(1188.9 – 796.9) = 796.2 kJ/kg
From interpolation in the tables at P = 60 bar & H = 796.2 kJ/kg → T = 206.5 K
59
Thermodynamic Analysis of Process
The basic of 2nd law states: ∆S ≥ 0. For a control volume at steady state flow process in surrounding at To:
Net rate of entropy Rate of entropy change

transport out by of surrounding
+ from ≥0
flowing streams heat transfer
Q surr
Whence: ( Sm
 ) fs  ≥0
To
   
Where: Q surr is negative with respect to the system, i.e. Qsurr  Q , the rate of entropy generation, S total
is:

Q
S total   ( Sm
 ) fs  ≥0 ……(1)
To
Q
S total  S  0 …….(2) per unit amount (mass) of fluid. The equality is for reversible
To
process
Ideal Work: It is the work resulting when the change of state of the fluid is accomplished completely
reversible. This is required:
(1) All changes within the control volume are reversible.

(2) Heat transfer to or from the surrounding is also reversible.
Note: A completely reversible process is hypothetical and has no entropy change.
Thus Eq. (1) becomes:
  T  ( Sm
Q  ) fs ……(3)
o
The energy Eq. is:
 1 
   Q  W s
 ( H  u 2  Zg ) m ……(4) substitute (3) in (4)
 2  fs

   To  ( Sm
1
 ( H  u 2  Zg )m  ) fs  W s (rev )
 2  fs
Where: W s (rev ) : the work for reversible process is called ideal work, W ideal .
 1 
→ W ideal  To  ( Sm ) fs   ( H  2 u  Zg )m 
2
…….(5)
  fs
For most application ∆EP and ∆EK are negligible. If there is one entrance and one exit and for unit mass of
fluid:
Wideal = To∆S - ∆H
60
Thermodynamic efficiency (ηt):

When Wideal (or W 
ideal ) is positive, it is the maximum work obtainable from a given change in the
properties of the flowing streams and is larger than Ws.
Ws
 t ( work produced ) 
Wideal
When Wideal (or W ideal ) is negative, it is the minimum work required to bring about a given change in the
properties of the flowing streams and is smaller than Ws.
Wideal
 t ( work required ) 
Ws
Ex: What is the maximum work that can be obtained in a steady state flow process from 1 mole of nitrogen
(assumed an ideal gas) at 800 K and 50 bar? Take the temperature and pressure of the surroundings 300 K
and 1.0133 bar.
Solution: Wmax = Wideal
Wideal = To∆S - ∆H ……(a)
∆H = CPmh(T2 – T1)
4000
From table (4.1) for nitrogen, and Tam = 550 K: CPmh/R = 3.28 + (0.0006)(550) + = 3.623
(800)(300)
→ ∆H = 3.623(8.314) (300 – 800) = - 15060 J/mol
T2 P
ln  R ln 2
∆S = CPms T1 P1
(550)(509.8)( 4000)
With Tlm = 509.8 K, CPms/R = 3.28 + 0.0006(509.8) + = 3.602
(800) 2 (300) 2
300 1.0133
∆S = 3.602(8.314) ln  8.314 = 3.042 J/mol.K
800 50
Substitute ∆H & ∆S in Eq. (a)
Wideal = (300)(3.042) – (-15060) = 15973 J/mol
Lost Work: It is the wasted work potential during a process as a result of irreversibilities and is defined as
the difference between the ideal work for a process and the actual work of the process.
  
W lost  Wideal  Ws ……….(6)
From Eqs. (4) & (5)

  ……..(7)
W lost  To  ( Sm) fs  Q

61
For one input and one output and per unit mass of fluid:
Wlost = To∆S – Q
Ex: Saturated vapor steam at 100 kPa (tsat = 99.63oC) is compressed adiabatically to 300 kPa. If the
compressor efficiency is 75%, what is the thermodynamic efficiency and what is the lost work if To = 300 K?
Wideal
Solution: In the compression process, the work is required; i.e.  t ( work required )  …..(a)
Ws
Ws = - ∆H = -(H2 – H1) ....(b)
From steam table for saturated vapor at 100 kPa: H1 = 2675.4 kJ/kg, S1 = 7.36 kJ/kg.K
For isentropic compression, S2 = S1 = 7.36 kJ/kg.K and at 300 kPa,
From steam table (superheated steam) H 2' = 2888.8 kJ/kg.K
 ∆HS = H 2' - H1 = 2888.8 – 2675.4 = 213.4 kJ/kg
H S 213.4
→ ∆H = = = 284.53 kJ/kg
 0.75
 from Eq. (b) Ws = - 284.53 kJ/kg
H2 = ∆H + H1 = 284.53 + 2675.4 = 2960 kJ/kg
From steam table, at H2 = 2960 and 300 kPa,
S2 = 7.5 kJ/kg.K → ∆S = S2 – S1 = 7.5 – 7.36 = 0.14 kJ/kg.K
Wideal = To∆S - ∆H = 300(0.14) – 284.5 = -242.5 kJ/kg
 242.5
From Eq. (a) ηt = = 0.852
 284.5
Since the compression is adiabatic: Wlost = To∆S
→ Wlost = 300(0.1421) = 42.6 kJ/kg
Or Wlost = Wideal – Ws = -241 – (284.5) = 42.6 kJ/kg
Note: The compressor efficiency η based on reversible compression to a final state where S2 = S1, is different
from the thermodynamic efficiency ηt which is based on reversible compression to the actual final state
where, S2 > S1.
The ideal gas mixture: A total thermodynamic property (nU, nH, nCP, nS, nA, or nG) of an ideal gas
mixture is the sum of the total properties of the individual species k, each evaluated at the mixture
temperature, T but at its own partial pressure, pk.
62
e.g. for volume V   y kVk

ig ig
……….(1)
Where V = molar volume of ideal gas mixture, Vkig = individual molar volume of pure species
ig
yk: mole fraction of species k in gas phase
H ig   y k H kig
For enthalpy ……(2)
But the enthalpy for an ideal gas is independent of pressure, i.e. H kig (T , pk )  H kig (T , P) .
Eq. (2) can be written as H   y k H k  0 this mean (enthalpy change of mixing is zero)
ig ig
For entropy S   y k S k  R  y k ln y k
ig ig
……(3)
1
Or S ig   y k S kig  R  y k ln
yk
On the left hand side is the entropy change, because yk ≤ 1, the right hand side then ≥ 0 and this agreement
with 2nd law.
For Gibbs energy of an ideal gas mixture, Gig = Hig – TSig , substitute for Hig and Sig from Eqs. (2) & (3);
G ig   y k H kig  T  y k S kig  RT  y k ln y k
Or G ig   y k Gkig  RT  y k ln yk ……(4)
The chemical potential of species k in an ideal gas mixture is defined as;
  (nG ig ) 
 kig    and is given by the Eq.:
 nk  P ,T ,ni
 kig  Gkig  RT  ln y k
Where: ni indicates that all mole numbers are held constant except the kth.
The ideal solution: Wherein all molecules are of the same size and all forces between molecules (like
and unlike) are equal.
For ideal solution: V   xkVk

id
Where: V id = molar volume of ideal solution, Vk = individual molar volume of pure species,
xk: mole fraction of species k in the liquid phase
Raoult's law: States that the partial pressure of species k in the vapor phase equal to the product of the
liquid phase mole fraction of species k and its vapor pressure at temperature T.
sat
i.e. ykP = xk Pk
sat
Where: P: total pressure, Pk : saturated vapor pressure of species k.
63
Bubble point temperature calculation:
Given the total pressure P and liquid composition, x1 & x2

sat sat
(1) Raoult's law: y1P = x1 P1 & y2P = x2 P2
sat sat
→ (y1 + y2)P = x1 P1 + x2 P2
sat sat
P = x1 P1 + x2 P2 ….(5)
sat sat
(2) P1 and P2 are given for each component by an equation called "Antoine equation" mathematically
as:
B
ln Pksat  A  ...…(6)
C T
Where: A, B, & C are constants and given for each component.
Substitute Eq. (6) in Eq. (5) and by trial and error (bubble point temp. is found).
(3) The vapor composition of each component can be calculated as:
Pksat xk
yk  …….(7)
P
Dew point temperature calculation:
Given the total pressure, P and vapor composition, yk:
y1 P
→ x1  P sat
sat
(1) Raoult's law: y1P = x1 P1 y1 P y2 P
1
x1 + x2 = sat +
y2 P P1 P2sat
→ x 2  P sat
sat
y2P = x2 P2
2
 y1 y2  n
yk
→ 1 = P  sat  sat  or 1 = P 
k 1 Pk
sat ……(8)
 P1 P2 
sat sat
(2) P1 and P2 are given for each component by an equation called "Antoine equation" mathematically
as:
B
ln Pksat  A  …… (9)
C T
Substitute Eq. (9) in (8) and by trial and error (dew point temp. is found).
The liquid composition can be calculated as:
64
yk P
xk 
Pksat
Bubble pressure calculation:
Given temperature, T and liquid composition, x1, x2, ….xn.
n
P   Pksat xk
k 1
Dew pressure calculation:
Given temperature, T and vapor composition, y1, y2, …..yn
1
P n
yk

k 1 Pk
sat
Ex: For the acetone(1)/ acetonitrile(2)/ nitromethane(3) system, we have the following Antoine equations:
2940.46
ln P1sat  14.5463  …(a)
T  237.22
2945.47
ln P2sat  14.2724  …(b)
T  224
2972.64
ln P3sat  14.2043  …(c)
T  209
Where T in oC and the vapor pressure are in kPa. Assuming that Raoult's law is approximate to this system,
calculate:
(a) P and yk, given that T = 80oC, x1 = 0.25, x2 = 0.35, and x3 = 0.4.
(b) P and xk, given that T = 70oC, y1 = 0.5, y2 = 0.3, and y3 = 0.2.
(c) T and yk, given that P = 80 kPa, x1 = 0.3, x2 = 0.45 and x3 = 0.25.
(d) T and xk, given that P = 90 kPa, y1 = 0.6, y2 = 0.2, and y3 = 0.2.
Solution: (a) A Bubble P calculation. For T = 80oC, the following vapor pressures are:
P1sat = 195.75 kPa, P2sat = 97.84 kPa, P3sat = 50.32 kPa
The P is calculated by P   xk Pk = 0.25(195.75) + 0.35(97.84) + 0.4(50.32) = 103.31 kPa

sat
xk Pksat
yk is calculated by y k 
P
0.25(195.75) 0.35(97.84) 0.4(50.32)
y1 = = 0.4737, y2 = = 0.3315, y3 = = 0.1948
103.31 103.31 103.31
(b) A Dew P calculation, for T = 70oC
65
1 1
P
P is calculated by y k = 0.5 0.2 = 74.27 kPa
 P sat 144.77  700..37
3

43.8
k
yk P
And xk is calculated by xk =
Pksat
0.5(74.27) 0.3(74.27) 0.2(74.27)
→ x1 = = 0.2565, x2 = = 0.3166, x3 = = 0.4269
144.77 70.37 43.8
(c) A Bubble T calculation:

sat sat sat
Using the equation: P = x1 P1 + x2 P2 + x3 P3 ….(d)
And from equations (a), (b), and (c):
2940.46
P1sat  Exp (14.5463  ) ….(e)
T  237.22
2945.47
P2sat  Exp(14.2724  ) ….(f)
T  224
2972.64
P3sat  Exp(14.2043  ) ….(g)
T  209
Substitute equations (e), (f), and (g) in Eq. (d)
2940.46 2945.47
→ 80 = (0.3) Exp(14.5463  ) + (0.45) Exp(14.2724  ) + (0.25)
T  237.22 T  224
2972.64
Exp (14.2043  )
T  209
By trial and error T is found → T = 68.6oC.

sat
At T = 68.6oC, Pk is calculated for each component from the equations (a), (b), and (c)
→ P1sat = 138.56 kPa, P2sat = 67.08 kPa, P3sat = 32.98 kPa
x k Pksat
yk is calculated by y k 
P
0.3(138.56) 0.45(67.08) 0.25(32.98)
→ y1 = = 0.5196, y2 = = 0.3773, y3 = = 0.1031
80 80 80
(d) A Dew T calculation:
n
yk  y1 y2 y3 
1 = P =P  sat  sat  sat  ….(h)
k 1 Pksat  P1 P2 P3 
66
Substitute Eqs. (e), (f), and (g) in Eq. (h)
 0 .6 0.2 0.2 
→ 1 = P 2940.46
 2945.47
 2972.64 
 Exp(14.5463  T  237.22 ) Exp(14.2724  T  224
) Exp(14.2043  T  209 
)

By trial and error → T = 73.95oC
At this T and from Eqs. (a), (b), and (c)
yk P
And xk is calculated by xk =
Pksat
0.6(90) 0.2(90) 0.2(90)
x1 = , x2 = , x3 = = 0.4457
163.47 80.37 40.39
Flash vaporization: is a vapor liquid equilibrium problem.
When a liquid under a pressure passes through a valve to a pressure low enough that some of liquid
vaporizes or flashes producing a two phase streams of vapor and liquid in equilibrium.
composition zi Vapor composition yi

Liquid V
F moles moles
Liquid composition xi
L moles
M.B.: on basis of 1 kmole of chemical species (F = 1):
1=L+V → L=1–V ….(1)
And zi F = xiL + yiV ….(2) (i = 1, 2, …N)
Substitute L from (1) in (2)
→ zi = xi(1 – V) + yiV …(3)

sat
From Raoult's law xi = yi/Ki …(4) where Ki = Pi /P
Substitute Eq. (4) in Eq. (3)
yi zi K i
→ zi = (1 – V) + yiV → yi = …(5)
Ki 1  V ( K i  1)
67
zi K i
Since ∑ yi = 1 →  1  V (K
 1)
=1 …(6)
i
In Eq. (6) T, P, and zi are known and V is unknown, so it is solve by trial and error, where V ≤ 1, yi then
found from Eq. (5) and xi is found from Eq. (4).
Ex: For the acetone(1)/ acetonitrile(2)/ nitromethane(3) system at 80oC and 110 kPa has the overall
composition, z1 = 0.45, z2 = 0.35, and z3 = 0.2. Determine L, V, xi, and yi.
Solution: It is unknown the system is in the two phase region. A two-phase system at a given temperature and
overall composition can exist from bubble point at Pb, where V = 0, and zi = xi, to the dew point at Pd, where
V = 1 and zi = yi. If the pressure lies between Pb and Pd then the system is in two phase region.
At 80oC the vapor pressure for each component are estimated as:
2940.46
ln P1sat  14.5463  → P1sat = 195.75 kPa
T  237.22
2945.47
ln P2sat  14.2724  → P2sat = 97.84 kPa
T  224
2972.64
ln P3sat  14.2043  → P3sat = 50.32 kPa
T  209
For Pb, zi = xi, → Pb = x1 P1sat + x2 P2sat + x3 P3sat = 0.45(195.75) + 0.35(97.84) + 0.2(50.32) = 132.4 kPa.
1
y y 1
For Pd, zi = yi, → Pd = y1 2 3 = = 101.52 kPa
P1sat

P sat

P sat
0.45
196.75  0.35
97.84  500..232
2 3
Since the pressure lies between Pb and Pd, it proceeds to the flash calculation.
zi K i
 1  V (K  1)
=1 …(a), Ki = Pi sat /P
i
K1 = 195.75/110 = 1.7795, K2 = 97.84/110 = 0.8895, K3 = 50.32/110 = 0.4575
0.45(1.7795) 0.35(0.8895) 0.2(0.4575)

Substitute K value in Eq. (a) → + + =1
1  V (0.7795) 1  V ( 0.1105) 1  V ( 0.5425)
By trial and error → V = 0.7364 mol, L = 1 – V = 0.2636
zi K i 0.45(1.7795)
yi = → y1 = = 0.5087, y2 = 0.339, and y3 = 0.1524
1  V ( K i  1) 1  0.7364(0.7795)
xi = yi/Ki → x1 = 0.5087/1.7795 = 0.2859, x2 = 0.339/0.8895 = 0.381, x3 = 0.1524/0.4575 = 0.3331
Partial molar properties:
  ( nM ) 
Mi   
 ni  P ,T ,nj
68
Where: M i is the partial molar property in the solution, may be partial molar volume in the solution, Vi ,
partial molar enthalpy in the solution, H i , partial molar entropy in the solution, S i …etc.
  ( nV ) 
e.g. Vi   n 
 i  P ,T ,nj
The molar solution property M is a sum of its parts M i .
=  xi M i
Mi.e. per unit mass or per unit mole.
Note: Solution properties M for example, U, H, S, G

Partial properties M i for example, U i , H i , S i , Gi
Pure-species properties Mi for example, Ui, Hi, Si, Gi
Ex: The need arises in the laboratory for 2000 cm3 of an antifreeze solution consisting of a 30 mole percent
solution of methanol in water. What volumes of pure methanol and of pure water at 25oC? Partial molar
volumes for methanol and water in a 30 mole percent methanol solution at 25oC are:
Methanol(1): V1 = 38.632 cm3/mol

Water(2): V2 = 17.765 cm3/mol
For pure species at 25oC: Methanol(1): V1 = 40.727 cm3/mol

Water(2): V2 = 18.068 cm3/mol
Solution: M= x M i i → V = x1 V1 + x2 V2 = 0.3(38.632) + 0.7(17.765) = 24.025 cm3/mol
Vt 2000
The total volume of solution is: Vt = nV → n = = = 83.246 mol
V 24.025
ni
xi = → n1 = x1 n = 0.3(83.246) = 24.974 mol
n
n2 = x2 n = 0.7(83.246) = 58.272 mol
The volume of each species is: Vi  niVi

t
→ V1t  n1V1 = 24.974 × 40.727 = 1017 cm3

V2t  n2V2 = 58.272 × 18.068 = 1053 cm3
Fugacity and Fugacity Coefficient:
Gibbs energy for constant composition fluid is dG = Vdp – SdT
At constant T → dG = Vdp
RT
For ideal gas: dGig = Vig dP = dP
P
69
Or dGig = RT d lnP (constant T) ….(1)
For real fluid: dG = RT d lnf (constant T) ….(2)
Where: f = fugacity: is a state function property so as chemical potential and is used to describe phase and
reaction equilibrium.
So the Fugacity is a pseudo pressure which when substituted for the pressure in the simple equations
derived for a perfect gas, enable then to be used for real gas without error. i.e. f ig =P.
f
Eq.(2) – (1): d(G – Gig) = RT d ln
P
f
But GR = G – Gig (residual property of Gibbs energy), and is a mixture property called Fugacity
P
coefficient and given the symbol  .
→ dGR = RT d ln  ....(3) (constant T), 
= f
P
Integrated Eq.(3) → GR (applied for mixture)
 ln 
RT
P
GR dP
But   ( Z  1)
RT 0 P
P
dP
→ ln    ( Z  1) ….(4)
0
P
For pure species i, dGi = RT d lnfi ...(5)

GR f
→ i  ln i , i  i
RT P
fˆ
For species i in solution î  i …..(6)
yi P
for ideal gas î = 1 → fî ig  yi P
And ln  =  xi ln î
Eq. (5) can be integrated from saturated liquid to saturated vapor:
fiv
G  G  RT ln l
V
i i
l
, but Gv = Gl
fi
→ fi  fi  fi ,
v l sat sat
where: f i indicates for either sat. vap. Or sat. liq.
f i sat
 isat  ….(7)
Pi sat
→ i  i   i
v l sat
Fugacity of species i as a compressed liquid:
70
dGi = RT d lnfi = Vi dP (constant T)

V
→ d lnfi = i dP
RT
Integration from the saturated liquid to compressed liquid:
P
fi 1
ln
f i sat
= RT  V dPi , since molar volume of liquid is a weak function of pressure
Pisat
fi Vi l ( P  Pi sat )
→ ln sat = , from Eq. (7) f i sat = isat Pi sat
fi RT
 V l ( P  Pi sat ) 
→ fi = isat Pi sat Exp  i  Used for liquids
 RT 
Fugacity of species i as a pure gas:
P = PCPr → dP = PC dPr substitute in Eq. (4)
Pr
dPr
→ ln  =  ( Z  1)
0
Pr
(constant Tr), but Z = Zo + ωZ1
Pr P
dPr r
1 dP
0 (Z  1) Pr   0 Z Prr
0
→ ln  =
Or ln  = ln  0 +ω ln  1 →  =  0 (  1 )ω
Ex: For H2O at temperature of 300oC and for pressure up to 10000 kPa plot values of fi and i versus P
calculated from data in the steam table.
Solution: As seen in steam table the condition of H2O start with superheated vapor at 300oC and 1 kPa
passes with saturation state (300oC & 8592.7 kPa) and ended with liquid water (300oC & 10000 kPa).
1
Start with Eq. d ln fi = dGi , Integration from low pressure reference (*) to the state pressure, P
RT
fi 1
ln *
 (Gi  Gi* ) , where: Gi = Hi – TSi and Gi*  H i*  TS i*
fi RT
f i 1  H i  H i* 
→ ln *
   ( S i  S i* ) ….(A) , for low enough pressure, f i * = P*
fi R T 
The lowest pressure at 300oC is 1 kPa, and the properties at these conditions:
H i* = 3076.8 kJ/kg, S i* = 10.34 kJ/kg
Eq. (A) is applied for states of superheated steam at 300oC for various values of pressure, from 1 kPa to the
saturation pressure, 8592.7 kPa.
e.g. for P = 4000 kPa and T = 300oC, Hi = 2962 kJ/kg, Si = 6.3642 kJ/kg.K
These values must be multiplied by MWH2O = 18 to convert to the molar properties:
71
fi 18  2962  3076.8 
Eq. (A) becomes ln * =   (6.3642  10.34)  = 8.1922
P 8.314  573.15 
→ fi/P* = 3612.5 , since P* = 1 kPa → fi = 3612.5 kPa, and
fi
i  = 3612.5/4000 = 0.9031
P
Similar calculations are achieved up to
Psat = 8592.7 kPa and plotting 7 in the 1
following figure, where, f i sat  6742.2 kPa. f i sat
and i = 0.7846.
sat 6 0.9
After saturated state, the H2O becomes liquid fi
5 0.8
 V l ( P  Pi sat )  isat
i.e. the Eq. fi = isat Pi sat Exp  i  is used
4 RT  fi=P 0.7
At 300oC Vi l = 1.404(18) = 25.29 cm3/mol
For P = 10000 kPa, 0.6
3
 25.29(10000  8592.7) 
fi = 0.785(8592.7)Exp   i
 8341(573) 
2
= 6792.7 kPa
f
i  i = 6792.7/10000 = 0.6793
1
P
Ex: Estimate the fugacity of the 1-butene vapor at 300oC and6 70 bar.
8
2 4
3
P×10 kPa
Solution: f =  P ….(a) but  =  0 (  1 )ω ……(b)
From Appendix B: TC = 419.6 K, PC = 40.2 bar, ω = 0.187
Tr = T/TC = 573.15/419.6 = 1.13, Pr = P/PC = 70/40.2 = 1.74
From figures (11.3) and (11.5)  o = 0.62 and  1 = 1.095
→ from Eq. (b)  = 0.62 (1.095)0.187 = 0.631
From Eq. (a) f = 0.631(70) = 44.17 bar
72

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Thermodynamics

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Biochemical Eng. Dept.

C.G.S ; centimeter, gram, second (Absolute units)

Newton’s 2nd Law of Motion: F = ma (N)

Where: F = force, m = mass of body, a = acceleration

Solution: F = ma = 250 × 10 = 2500 N

°F = 32.0 + 1.8 ×oC

Density, ρ: is the reciprocal of specific volume or molar volume.

Pgage = Pabs - Patm

Pvac = Patm - Pabs

Pabs = Patm - Pvac = 14.5 - 5.8 = 8.7 psi

Solution: Pabs =Pgage + Patm

 Pabs = 4.6 + 96 = 100.6 kPa

Work: Work W is done whenever a force acts through a distance.

dW = Fdl where F = force and dl = displacement

Consider a compression or expansion of fluid in a cylinder:

Energy: It is defined as the capacity of a system to perform work or produce heat.

Forms of energy: mechanical, electrical, chemical, heat, light ….. etc.

Kinetic energy: (EK) is the energy of motion.

dW = Fdl = ma dl , but a = du/dt

Potential energy: EP is defined as the energy of position.

W = Fdl =F(z2 – z1) = mg(z2 – z1)

Thus EP = mzg (N.m) or Joules

In English unit EP = mzg/gc (ft.lbf)

50 lbm  100 ft  32.17 ft / s 2

Note: For a freely falling body :  EK +  EP = 0

BTU (British thermal unit) 1 BTU = 1055 J 1 calorie = 4.184 J

FE = force × distance = F× L (N.m)

Zeroth law of thermodynamics: states that if two bodies are in thermal

Boundary: The envelope (Real or imaginary) which contains the system.

Surrounding: It is any thing out of the system.

Closed system: It is a region that of constant mass and no mass

integrated lead to finite difference. i.e.  dT = T2 – T1 and  dU  U

The formulation of 1st law of thermodynamics:

Δ (energy of the system) + Δ (energy of surrounding) = 0

Δ (energy of the system) = ΔU + ΔEK + ΔEP …..(1)

Δ (energy of surrounding) = ± Q ± W …..(2)

So summing 1 & 2 ΔU + ΔEK + ΔPK ± Q ± W = 0

The sign of Q and W

i.e. ΔU + ΔEK + ΔEP = Q – W

ΔU = Q – W (joules) in SI system but in English system (calorie, ft-lbf or BTU).

Solution: there is no ΔEK and ΔEP so ΔU = Q – W

U1 = 800 kJ , U2 = ? Q = - 500 kJ, W = - 100 kJ

Now U2 – 800 = -500 – (- 100)

Solution: Assume only internal energy is change in the system P

 ΔUab = Qacb – Wacb

ΔUab = 60 = Qaeb – Waeb = Qaeb – 20 c d

→ Qbda = - 90 J [i.e. heat is liberate]

Steady state flow process:

For sections 1 & 2 and unit mass of fluid:

The total work of the system W is equal to z2

 Eqn (2) becomes

Air 1bar, Air 1 bar,

→ Q = - 60000 J/kg or Q = - 60 kJ/kg

Negligible the velocity in sections 1 & 2, i.e.

→H2 = 68.47 BTU/lbm

From steam table at H = 68.47 BTU/lbm , T = 100.74oF

The Reversible Process:

Notation; constant-volume and constant-pressure processes:

The W for mechanically, reversible, non-flow process is

Eqn (1) becomes d(nU) = dQ –P d(nV) …..(2)

at constant volume d(nV) = 0

 Eqn (2) becomes: d(nU) = dQ

From enthalpy definition and for n moles