Chemical Engineering

Thermodynamics – I
ChE–214
Aqeel Ahmad TAIMOOR
 Class Objectives
 Understand Ideal Gas Postulates

 Understand different processes of Ideal gas

 Calculate the entropy function for an ideal gas

 Understand the entropy change for a process

 Understand the Lost Work and its relation to entropy

 Understand the work function, Helmholtz energy and

Gibbs energy
 Class Objectives
 Understand Ideal Gas Postulates

 Understand different processes of Ideal gas

 Calculate the entropy function for an ideal gas

 Understand the entropy change for a process

 Understand the Lost Work and its relation to entropy

 Understand the work function, Helmholtz energy and

Gibbs energy
 Ideal Gas
 Ideal gas cannot be liquefied
 Ideal gas molecules does not have any volume, as its volume
becomes zero at 0 K.
 Ideal gas is the one having no molecular interactions
 Ideal gas molecules have elastic collision
 Ideal gas follows the following law
 PV = RT
 U = f(T)
 H = f(T)
 Ideal Gas
 Furthermore no matter what is the process only for ideal
gas it is always true that

 dU = CVdT

 dH = CPdT

 dH = dU + RdT

 CP = CV +R
 Class Objectives
 Understand Ideal Gas Postulates

 Understand different processes of Ideal gas

 Calculate the entropy function for an ideal gas

 Understand the entropy change for a process

 Understand the Lost Work and its relation to entropy

 Understand the work function, Helmholtz energy and

Gibbs energy
Isothermal Process-Ideal Gases
 T = constant

 dU = dH = 0

 Q+W=0

 W = RT ln(P2/P1) = –RT ln(V2/V1)

 Q = –RT ln(P2/P1) = RT ln(V2/V1)

Isobaric Process-Ideal Gases
 P = constant

 dU = CVdT; dH = CPdT

 dQ + dW = CVdT

 W = –P(V2-V1)

 Q = ∫CVdT + P(V2-V1)

 Q = ∫CPdT
Isochoric Process-Ideal Gases
 V = constant

 dU = CVdT; dH = CPdT

 dQ + dW = CVdT

 W=0

 Q = ∫CVdT
Adiabatic Process-Ideal Gases
 Q=0

 dU = CVdT; dH = CPdT

 dQ + dW = CVdT

 0 – PdV = CVdT

 -R/CV (dV/V) = dT/T

 T2/T1 = (V1/V2)R/CV

 T2/T1 = (P2/P1)R/CP

 P2/P1 = (V1/V2)CP/CV
Adiabatic Process-Ideal Gases
 If γ= CP/CV
 Then
 T2/T1 = (V1/V2)R/CV
 T2/T1 = (V1/V2) γ-1
 Or TVγ-1 = constant
 TP(1-γ)/γ= constant
 PVγ= constant
 Expressions are only valid for Ideal gas and for constant
heat capacities + reversible process
Adiabatic Process-Ideal Gases
 dW = CVdT; W = CVΔT = RΔT/(γ-1)

 W = (RT2 – RT1)/(γ-1) = (P2V2 – P1V1)/(γ-1)

 As PVγ = constant; therefore

 V2 = (P1/P2)1/γV1

 So W =(P2(P1/P2)1/γV1 – P1V1)/(γ-1)

 Or W = P1V1/(γ-1)((P2/P1) (γ-1)/γ-1)

 W = RT1/(γ-1)((P2/P1) (γ-1)/γ-1)
Polytropic Process-Ideal Gases
 PVδ = constant

 dW = -PdV

 W = P1V1/(δ-1)((P2/P1) (δ-1)/δ-1)

 W = RT1/(δ-1)((P2/P1) (δ-1)/δ-1)

 Q + W = ΔU
éæ ö(d -1)/d ù
(d - g )RT1 ê P2
Q= ç ÷ -1ú
(d -1)(g -1) êëè P1 ø úû
 Ideal gas processes
 PVδ = constant

 Isobaric means constant P; δ = 0

 Isothermal Process means constant T

 P (RT/P)δ = P1-δRδTδ = constant; δ = 1

 Adiabatic Process means Q = 0; δ = γ

 Isochoric Process means constant V

 PVδ = constant; P1/δV = constant1/δ; δ = ±∞

Polytropic Processes-Ideal Gas
 Problem
Air is compressed from an initial state of 1 bar and 298 K to a
final state of 5 bar and 298 K by three different mechanically
reversible processes in a closed system:
a. Heating at constant volume followed by cooling at constant
pressure
b. Isothermal compression
c. Adiabatic compression followed by cooling at constant
volume
Assume air to be an ideal gas with the constant heat capacities
Cv= 5/2R and Cp=7/2R. Calculate the work required, heat
transferred, and the changes in internal en.ergy and enthalpy of
the air for each process
 Problem
An ideal gas undergoes the following sequence of
mechanically reversible processes in a closed system
a. From an initial state of 343 K and 1 bar, it is compressed
adiabatically to 423 K
b. It is then cooled from 423 K to 343 K at constant
pressure
c. Finally it is expanded isothermally to its original state
Calculate W, Q, ΔU, ΔH for each of the three processes and
for the entire cycle. Take Cv = 3/2R and Cp = 5/2R
 Problem
If the process of previous problem are carried out
irreversibly but so as to accomplish exactly the same changes
of state 0 the same changes in P, T, U and H then different
values of Q and W results. Calculate Q and W if each step
is carried out with an efficiency of 80%
 Problem
Air flows at a steady rate through a horizontal pipe to a partly
closed valve. The pipe leaving the valve is enough larger than the
entrance pipe that the kinetic-energy change of the air as it flows
through the valve is negligible. The valve and connecting pipes are
well insulated. The conditions of the air upstream from the valve
are 20°C (293.15 K) and 6 bar, and the downstream pressure is 3
bar. If air is regarded as an ideal gas, what is the temperature of
the air some distance downstream from the valve?
 Problem
A compressed-air tank is to be repressurized to 40 bar by being
connected to a high-pressure line containing air at 50 bar and
20°C. The repressurization of the tank occurs so quickly that the
process can be assumed to be adiabatic; also, there is no heat
transfer from the air to the tank. For this illustration, assume air to
be an ideal gas with Cv = 21J/mol/K.

a. If the tank initially contains air at 1 bar and 20°C, what will
be the temperature of the air in the tank at the end of the
filling process?

b. After a sufficiently long period of time, the gas in the tank is

found to be at room temperature (20°C) because of heat
exchange with the tank and the atmosphere. What is the new
pressure of air in the tank?
 Problem
A compressor is a gas pumping device that takes in gas at
low pressure and discharges it at a higher pressure. Since this
process occurs quickly compared with heat transfer, it is
usually assumed to be adiabatic; that is, there is no heat
transfer to or from the gas during its compression. Assuming
that the inlet to the compressor is air (which we will take to
be an ideal gas) with Cp = 29 J/mol/K at 1 bar and 290 K
and that the discharge is at a pressure of 10 bar, estimate the
temperature of the exit gas and the rate at which work is
done on the gas (i.e., the power requirement) for a gas flow
of 2.5 mol/s.
 Problem
A gas cylinder of 1 m3 volume containing nitrogen initially
at a pressure of 40 bar and a temperature of 200 K is
connected to another cylinder of 1 m3 volume that is
evacuated. A valve between the two cylinders is opened until
the pressures in the cylinders equalize. Find the final
temperature and pressure in each cylinder if there is no heat
flow into or out of the cylinders or between the gas and the
cylinder. You may assume that the gas is ideal with a
constant-pressure heat capacity of 29.3 J/(mol K).
 Class Objectives
 Understand Ideal Gas Postulates

 Understand different processes of Ideal gas

 Calculate the entropy function for an ideal gas

 Understand the entropy change for a process

 Understand the Lost Work and its relation to entropy

 Understand the work function, Helmholtz energy and

Gibbs energy
 Entropy Calculations
 dQ = dU – dW

 dQ = d(H – PV) – PdV

 dQ = dH – VdP

 dQ/T = dH/T – VdP/T

 dS = CP/T dT – ZRdP/P
 Problem
Methane gas at 550 K and 5 bar undergoes a reversible
adiabatic expansion to 1 bar. Assuming methane to be an
ideal gas at these conditions, find its final temperature.
 Class Objectives
 Understand Ideal Gas Postulates

 Understand different processes of Ideal gas

 Calculate the entropy function for an ideal gas

 Understand the entropy change for a process

 Understand the Lost Work and its relation to entropy

 Understand the work function, Helmholtz energy and

Gibbs energy
 Entropy change for the
processes
 For an engine let

 ΔSH = - QH/TH (Change in entropy for hot reservoir)

 ΔSC = QC/TC (Change in entropy for cold reservoir)

 Total change is entropy

 ΔST = ΔSH + ΔSC = - QH/TH + QC/TC

 Total entropy change by second law of thermodynamics

must be 0 or positive.

 QH/TH =< QC/TC

 Entropy change for the
processes
 QH/TH =< QC/TC

 QH/TH = QC/TC (Process is reversible)

 QH/TH < QC/TC (Process is irreversible)

 Problem
A 40-kg steel casting (Cp = 0.5 kJ/kg/K) at a temperature
of 450°C (723.15 K) is quenched in 150 kg of oil (Cp = 2.5
kJ/kg/K) at 25°C (298.15 K). If there are no heat losses,
what is the change in entropy of

(a) the casting,

(b) the oil, and

(c) Both considered together

 Problem
In a steady-state flow process, 1 mol/s of air at 600 K
(326.85°C) and 1 atm is continuously mixed with 2 mol/s of
air at 450 K (176.85°C) and 1 atm. The product stream is at
400 K (126.85°C) and 1 atm. Determine the rate of heat
transfer and the rate of entropy generation for the process.
Assume that air is an ideal gas with Cp = (7/2)R, that the
surroundings are at 300 K (26.85°C), and that kinetic- and
potential-energy changes are negligible.
 Problem
An inventor claims to have devised a process which takes in
only saturated steam at 100°C (373.15 K) and which by a
complicated series of steps makes heat continuously
available at a temperature level of 200°C (473.15 K), where
2000 kJ of energy as heat is liberated for every kilogram of
steam taken into the process. Show whether or not this
process is possible. To give this process the most favourable
conditions, assume cooling water available in unlimited
quantity at a temperature of 0°C (273.15 K).
 Class Objectives
 Understand Ideal Gas Postulates

 Understand different processes of Ideal gas

 Calculate the entropy function for an ideal gas

 Understand the entropy change for a process

 Understand the Lost Work and its relation to entropy

 Understand the work function, Helmholtz energy and

Gibbs energy
 Lost Work
 If process is irreversible then

 Wideal + Wl = ΔH – Q

 Now Wideal = ΔH – TaΔS

 Wl – TaΔS = – Q

 For irreversible process

 Total entropy change is positive (say Sg)

 Sg = ΔSProcess + ΔSSurroundings

 Sg = ΔSProcess – Q/Ta
 Lost Work
 Sg = ΔSProcess – Q/Ta

 ΔSProcess = Sg + Q/Ta

 Wl – TaΔSProcess = – Q

 Wl = TaSg
Problem
Example Continued..
Clausius Statement of the Second Law

The second-law statement of Rudolf Clausius (1822–1888)

is that it is not possible to construct a device that operates in
a cycle and whose sole effect is to transfer heat from a colder
body to a hotter body. Show from the axiom Sgen ≥ 0 that
the process below is impossible, so that the Clausius
statement of the second law is consistent with what has been
presented in this book.
 Problem
Compute the entropy generated on mixing 1 kg of steam at
1 bar and 200°C (state 1) with 1 kg of steam at 1 bar and
300°C (state 2).
 Problem
Compute the entropy generated by the flow of 1 kg/s of
steam at 400 bar and 500°C undergoing a Joule-Thomson
expansion to 1 bar.
 Problem
An engineer claims to have invented a steady-flow device
that will take air at 4 bar and 20°C and separate it into two
streams of equal mass, one at 1 bar and −20°C and the
second at 1 bar and 60°C. Furthermore, the inventor states
that his device operates adiabatically and does not require
(or produce) work. Is such a device possible? [Air can be
assumed to be an ideal gas with a constant heat capacity of
Cp=29.3J/mol / K ].
 Problem
A steam turbine operates at the following conditions:

a. Compute the horsepower developed by the turbine and the

entropy change of the steam.

b. Suppose the turbine is replaced with one that is well insulated,

so that the heat loss is eliminated, and well designed, so that
the expansion is reversible. If the exit pressure and velocity are
maintained at the previous values, what are the outlet steam
temperature and the horsepower developed by the turbine?
 Problem
What is the maximum work that can be obtained from
steam at 2 MPa and 700°C that is flowing continuously at 5
m/sec in a pipe that is 5 m above ground level?
 Problem
One continuously flowing stream of steam is at 2 MPa and
800°C, and another is at 1 MPa and 900°C. Which could, in
principle, produce the greatest amount of useful work in a
flow process?
 Problem
What is the maximum work that can be obtained from
steam at 2 MPa and 700°C in a non-flow process?
 Class Objectives
 Understand Ideal Gas Postulates

 Understand different processes of Ideal gas

 Calculate the entropy function for an ideal gas

 Understand the entropy change for a process

 Understand the Lost Work and its relation to entropy

 Understand the work function, Helmholtz energy and

Gibbs energy
 Helmholtz Energy

Free (available) energy for a closed system (batch

reactor/closed system) with constant volume (Liquid phase)
and constant temperature (isothermal)

 Mathematically

 F or A = U – TS
 Gibbs Energy

 Constant volume and isothermal processes are limited so

the up-gradation comes as Gibbs Energy

 G = H – TS
Mnemoic
 Class Objectives
 Understand Ideal Gas Postulates

 Understand different processes of Ideal gas

 Calculate the entropy function for an ideal gas

 Understand the entropy change for a process

 Understand the Lost Work and its relation to entropy

 Understand the work function, Helmholtz energy and

Gibbs energy