Chemical Engineering

Thermodynamics Lecture
Scope of Lecture
• Applications of First Law
• Applications of Second Law
• Thermodynamic Flow Processes / Gas Cycles and
Refrigeration

What’s not included

• X Zeroth Law of Thermo
• X Flows in Ducts / Nozzles
• X PVT relations of Real Fluids
• X Heat Effects
• X Solution Thermodynamics
Basic Terminologies
Thermodynamics is the science that deals with the study of energy
transformation and the relationships of the physical properties of
substances that are affected by these transformations.
The first step in any thermodynamic analysis must be the selection of
the system, its boundaries, and its surroundings.
There are three types of thermodynamic systems:
1. Open system – a thermodynamic system for which there is exchange
of energy and matter with the surroundings
2. Closed system – a thermodynamic system for which there is only
exchange of energy with the surroundings, but the mass of the system
remains constant
3.Isolated System, which can be differentiated into
• Thermally isolated system where there is no exchange of energy and
matter with the surroundings, and
• Mechanically isolated system where there is no work done on the
system or by the system
Basic Terminologies
• Phase : state of agglomeration of the system, e.g. gas, liquid, or solid.
• Extensive Variable : those variables that are dependent on the amount
of matter in the system. Examples are volume, heat capacity
• Intensive Variable : those variables that are independent of the amount
of matter in the system. Examples are viscosity, temperature, and
pressure
• State Functions : macroscopic quantities that are dependent only on
the initial and final state of the thermodynamic system, and
independent of the process taken by the system, eg. P, V, T, H, U, G, S,
• Path Function : macroscopic quantities that are dependent on the
process taken by the system, eg. Q, W.
• Thermal Reservoir: reservoir, a special kind of system that always
remains at constant temperature even through energy or removed by
heat transfer.
Sample Problem
Liquid water at 180°C and 1002.7 kPa has an internal energy (on an
arbitrary scale) of 762.0 kJ⋅kg−1 and a specific volume of 1.128
cm3⋅g−1.
(a) What is its enthalpy?
(b) The water is brought to the vapor state at 300°C and 1500 kPa,
where its internal energy is 2784.4 kJ⋅kg−1 and its specific volume is
169.7 cm3⋅g−1. Calculate ΔU and ΔH for the process.
Solution for a
Given :T1 = 1800C, P1 = 1002.7kPa, U1 = 762.0 kJ/kg, v1 = 1.128 cm3/g
Required : H1

To get H1; H1 = U1 + P1* v1

v1 = 1.128 cm3/g → 1.128 x10-3 m3/kg
H1 = 762.0 kJ/kg + 1002.7kPa * 1.128 x10-3 m3/kg
H1 = 763.13 kJ/kg
Solution for b
Given : T2 = 3000C, P2 = 1500kPa, U2 = 2784.4 kJ/kg, v2 = 169.7 cm3/g
Required : ∆H, ∆U

To get ∆H; H2 = U2 + P2* v2

v2 = 169.7 cm3/g → 0.1697 m3/kg
H2 = 2784.4 kJ/kg + 1500kPa * 0.1697 m3/kg
H2 = 3038.95 kJ/kg
∆H = H2 – H1
∆H = (3038.95 – 763.13 ) kJ/kg
∆H = 2275.82 kJ/kg
To get ∆U, ∆U= U2 - U1 = 2784.4 kJ/kg - 762.0 kJ/kg
∆U = 2022.4 kJ/kg
Practice Problem
One gram of water having a volume of 1 cm3 becomes 1671 cm3 of
steam when boiled at a constant pressure of 1 atm. The heat of
vaporization at this pressure is 2256J/g. What is the increase in internal
energy?
(ANS. 2087J/g)
First Law of Thermodynamics
• The first law of thermodynamics is a statement of the conservation of
energy, i.e. energy cannot be created nor destroyed, it can only be
converted from one form into another. As a consequence, this law
states that the energy of the thermodynamic universe is constant
Sample Problem
Fifty (50) kmol per hour of air is compressed from P1 = 1.2bar
to P2 = 6.0 bar in a steady flow compressor. Delivered
mechanical power is 98.8kW.

Temperatures and velocities are:

T1 = 300K; T2 = 520K
u1 = 10m/s; u2 = 3.5m/s;

Estimate the rate of heat transfer from the compressor.

Assume for air that Cp = 7/2 R and that enthalpy is
independent of pressure.
Solution
Given : 𝑛ሶ = 50kmol/h → 13.89 mol/s
Cp = 7/2 R R = 8.3145 J/mol-K

Required : 𝑸ሶ

Using Energy Balance: 𝑄ሶ + 𝑊𝑠

ሶ = ∆Hሶ + ∆KE
ሶ + ∆PE
ሶ , ∆Hሶ = n*Cp * (T2 - T1)
ሶ =0
∆PE
∆Hሶ = 13.89 mol/s* 7/2 *(8.3145)J/mol-K*(520-300)K
𝑊𝑠 ሶ = 98.8x10^3 W
∆Hሶ = 88926.072 J/s or 88926.072 W

∆KE = ½ [(u2)2-(u1)2]
∆KE ሶ = ½ 𝑚ሶ [(u2)2-(u1)2] 𝑄ሶ + 98.8x10^3 = 88926.072 + -17.67 W
ሶ = ½ * 13.89mol/s * 29x10-3 kg/mol *[(3.5)2-(10)2]m2/s2
∆KE 𝑄ሶ = -9891.59 W = -9.89W
∆KEሶ = -17.67 W
Practice Problem
• Water flows through a horizontal coil heated from the outside by high-temperature flue gases. As it passes
through the coil, the water changes state from liquid at 200 kPa and 80°C to vapor at 100 kPa and 125°C. Its
entering velocity is 3 m⋅s−1 and its exit velocity is 200 m⋅s−1. Determine the heat transferred through the
coil per unit mass of water. (Ans. 2411.6 kJ/kg)
Principle of Reversibility
 Equations of Reversibility for Ideal Gas

n = 0, isobaric
n = 1, isothermal
n = γ, reversible adiabatic
n = infinity, isochoric
Sample Problem
• One mole of ideal CH4 is contained in a leak proof piston cylinder
assembly at 8bar and 1000K. The gas undergoes isothermal expansion
to 4 bar under reversible conditions. The heat transferred during the
process is
Solution
Given : n = 1 mol
Isothermal expansion P2 = 4 bar
P1 = 8 bar
reversible
T1 = 1000K

Required : Q

W = - ‫𝑉𝑑𝑃 ׬‬
𝑛𝑅𝑇
=-‫׬‬ 𝑑𝑉
𝑉
1
= -nRT ‫𝑉𝑑 𝑉 ׬‬
𝑉
= -1mol*8.3145 J/mol-K*1000K*ln (𝑉2 )
1
𝑃
= -1mol*8.3145 J/mol-K*1000K*ln (𝑃1)
2
W = -5763.17 J
Q = 5763.17 J
Practice Problem
5kmol of water vapor at 1000C and 1 atm is compressed isobarically from initial volume of 153L to form liquid
at 1000C. Calculate the work if it is reversible and the gas is ideal. (Ans. 6kJ)

What is most nearly the resulting pressure when 400g of air at 103.6kPa and 930C is heated at constant V to
4270C. Assume ideality. Compute the change in internal energy if Cp = 7/2*R
(Ans. P2=200kPa, ∆U = 95.8kJ)
Sample Problem
• One cubic meter of an ideal gas at 600 K and
1000 kPa expands to five times its initial volume
as follows:

• (a) By a mechanically reversible, adiabatic

process.
• (b) By an adiabatic, irreversible process in which
expansion is against a restraining pressure of 100
kPa.

For each case calculate the final temperature,

pressure, and the work done by the gas. Cp = 21
J/mol/K
 Solution part a
Given :
P1 = 1000 kPa P2 = ??
Ideal gas, adiabatic
T1 = 600K T2 = ??
Reversible, Cp = 21 J/mol-K
V1 = 1m3 V2 = 5m3

Required : P2, T2, W

P1*V1γ = P2*V2γ 𝑃1 ∗𝑉1 𝑃2 ∗𝑉2 Q + W = ∆𝑈

=
Cp = 21 J/mol-K 𝑇1 𝑇2
𝑄=0
Cv = Cp-R ∆𝑈 = Cv * (T2 - T1)
1000𝑘𝑃𝑎 ∗1 𝑚3 69.635𝑘𝑃𝑎∗5 𝑚3
Cv = 12.6855 J/mol-K = W = Cv * (T2 - T1)
600𝐾 𝑇2
γ = Cp/Cv = 1.655 W = 12.6855 J/mol-K *(209.085-600)K
1000kPa*11.655 = P2*51.655 W = -4958.95 J/mol
T2 = 209.085K
P2 = 69.695 kPa n = P1* V1/RT → n = 200.45 mol
Then W = -994036.97 J
 Solution part b
Given :
P1 = 1000 kPa P2 = ??
Ideal gas, adiabatic
T1 = 600K T2 = ??
Irreversible
V1 = 1m3 Pext = 100kPa V2 = 5m3

Required : P2, T2, W

Q + W = ∆𝑈 𝑃1 ∗𝑉1 𝑃2 ∗𝑉2
W = -Pext ∗ ∆𝑉 =
𝑇1 𝑇2
W = -100x103Pa *(5-1)m3 ∆𝑄 = 0, W = ∆𝑈
W= Cv * (T2 - T1) 1000𝑘𝑃𝑎 ∗1 𝑚3 𝑃 ∗5 𝑚3
2
W =-400x103J 600𝐾
=442.695 𝐾
W= nCv * (T2 - T1)
-400x103J = 200.45 mol* 12.6855 J/mol-K P2 = 147.565K
*(T2 -600)K
T2 = 442.695 K
Practice Problem
One mole of an ideal gas with Cp = (7/2)R and CV = (5/2)R expands from P1 = 8 bar and T1 = 600 K to P2 = 1 bar by each of the
following paths:
(a) Constant volume;
(b) Constant temperature;
(c) Adiabatically.
Assuming mechanical reversibility, calculate W, Q, ΔU, and ΔH for each process.

Ans. A.) Q = ΔU = -10.91 kJ/mol;

ΔH = -15.28 kJ/mol
W=0
B.) ΔH = ΔU = 0;
-Q = W = -10.37 kJ/mol
C.) Q = 0;
ΔU = W = -5.586 kJ/mol
ΔH = -7.821 kJ/mol
Applications of Second Law
Statements of the Second Law
Application of Second Law to Heat Engines
• A heat engine is a device that takes in energy by heat
and, operating in a cyclic process, expels a fraction of
that energy by means of work. For instance, in a typical
process by which a power plant produces electricity, a
fuel such as coal is burned and the high-temperature
gases produced are used to convert liquid water to
steam. This steam is directed at the blades of a turbine,
setting it into rotation. The mechanical energy associated
with this rotation is used to drive an electric generator.

A heat engine carries some working substance through a cyclic

process during which (1) the working substance absorbs energy by
heat from a high-temperature energy reservoir, (2) work is done by
the engine, and (3) energy is expelled by heat to a lower-temperature
reservoir. As
Thermal efficiency of a heat engine
Carnot Engine
• In 1824, a French engineer named Sadi Carnot described a theoretical engine, now called a Carnot engine,
that is of great importance from both practical and theoretical viewpoints.
• He showed that a heat engine operating in an ideal, reversible cycle—called a Carnot cycle—between two
energy reservoirs is the most efficient engine possible.

• Such an ideal engine establishes an upper limit on the efficiencies of all other engines. That is, the net
work done by a working substance taken through the Carnot cycle is the greatest amount of work possible
for a given amount of energy supplied to the substance at the higher temperature.

• Carnot’s theorem can be stated as follows:

Efficiency in Carnot Engine
• Efficiency of Carnot Engine
Sample Problem
A nuclear power plant generates 750 MW; the reactor temperature is
315°C and a river with water temperature of 20°C is available.
(a) What is the maximum possible thermal efficiency of the plant, and
what is the minimum rate at which heat must be discarded to the
river?
(b) If the actual thermal efficiency of the plant is 60% of the maximum,
at what rate must heat be discarded to the river, and what is the
temperature rise of the river if it has a flow rate of 165 m3·s–1 ?
 Solution to part a
Given :
Power Generated= -750 MW
Reactor Temp = 3150C
River Temp = 200C

Required : maximum efficiency, ƞmax

: Minimum Heat Discarded
Minimum Heat Discarded = 𝑄′𝑐ሶ
𝑇
Ƞmax = Ƞcarnot = 1-𝑇 𝑐 ሶ
Maximum Heat Required = 𝑄′ℎ
𝐻
𝑊ሶ
Ƞmax = 𝑄′ℎ
ሶ
20+273.15 𝐾
Ƞmax = 1-
315+273.15 𝐾
𝑊ሶ = −750𝑀𝑊, Ƞmax = 0.5015
ሶ = 1495.51 MW
Therefore 𝑄′ℎ
ሶ − 𝑄′𝑐
𝑊ሶ = 𝑄′ℎ ሶ -→ 750MW = 1495.51 MW - 𝑄𝑐ሶ
Ƞmax = 0.5015
ሶ = 745.51MW
𝑄′𝑐
Solution to part b
Given :
W= -750 MW 𝑉ሶ of the river= 165 m3/s
TH= 3150C
TC= 200C
actual efficiency, ƞ = 60% of the maximum

Required : Actual heat rejected, 𝑸𝒄ሶ

: Temperature Rise, ∆T

Ƞ = 0.6*Ƞmax = 0.6*0.5015
Ƞ = 0.3 𝑄𝑐ሶ = 𝑚ሶ Cp*∆T
𝑊ሶ −750𝑀𝑊 𝑄𝑐ሶ = 𝑉ሶ * ρ*Cp*∆T
Ƞ= 𝑄ℎሶ → 0.3 = 𝑄ℎሶ
1750 x106W = 165 m3/s * 1000 kg/m3 *4184 J/kg –K * ∆T
Therefore, 𝑄ℎሶ = 2500MW
∆T = 2.53K
𝑊ሶ = 𝑄ℎሶ − 𝑄𝑐ሶ -→ 750MW = 2500 MW - 𝑄𝑐ሶ
𝑄𝑐ሶ = 1750MW
Practice Problems
A particular power plant operates with a heat-source reservoir at 623.15 K (350°C) and a heat-sink reservoir at
303.15 K (30°C). It has a thermal efficiency equal to 55% of the Carnot-engine thermal efficiency for the same
temperatures.

(a) What is the thermal efficiency of the plant? Ans. 0.282

(b) To what temperature must the heat-source reservoir be raised to increase the thermal efficiency of the
plant to 35%?. Ans. Th =833.66K
Second Law and the Concept of Entropy and Disorder

• The zeroth law of thermodynamics involves the concept of

temperature, and the first law involves the concept of internal energy.
Temperature and internal energy are both state variables; that is, the
value of each depends only on the thermodynamic state of a system,
not on the process that brought it to that state. Another state
variable—this one related to the second law of thermodynamics—is
entropy.
• As we have just seen, the flow of energy as heat does not indicate
whether or not a process will occur spontaneously. Entropy describes
this spontaneity
Spontaneity
• proceeding from natural feeling or
native tendency without external
constraint
Spontaneity and Entropy
• One way of conceptualizing a change in entropy is to relate it to
energy spreading. A natural tendency is for energy to undergo
spatial spreading in time, representing an increase in entropy.

• If a basketball is dropped onto a floor, it bounces several times

and eventually comes to rest. The initial gravitational potential
energy in the basketball–Earth system has been transformed
to internal energy in the ball and the floor. That energy is
spreading outward by heat into the air and into regions of the
floor farther from the drop point. In addition, some of the
energy has spread throughout the room by sound. It would be
unnatural for energy in the room and floor to reverse this
motion and concentrate into the stationary ball so that it
spontaneously begins to bounce again.
• In the adiabatic free expansion, the spreading of energy
accompanies the spreading of the molecules as the gas rushes
into the evacuated half of the container. If a warm object is
placed in thermal contact with a cool object, energy transfers
from the warm object to the cool one by heat, representing a
spread of energy until it is distributed more evenly between
the two objects.
Mathematical Representation

(General Formula)

For an isothermal expansion of an Ideal Gas -

Entropy and Ideal Gas
Sample Problem
One mole of an ideal gas is compressed isothermally but irreversibly at
130°C from 2.5 bar to 6.5 bar in a piston/cylinder device. The work
required is 30% greater than the work of reversible, isothermal
compression. The heat transferred from the gas during compression
flows to a heat reservoir at 25°C.

Calculate the entropy changes of the gas, the heat reservoir, and
ΔStotal.
 Solution
Given :
n = 1 mol P2 = 6.5 bar
isothermal
T1 = 1300C T2 = 1300C
Irreversible
P1 = 2.5 bar Actual Work is 30%
T surr = 25oC Greater than in Reversible Work

Required : ∆Sg, ∆Sres , ∆Stotal

Since gas is ideal, we can use : To get the change in entropy of 1

W = -nRT ‫𝑉𝑑 𝑉 ׬‬
𝑇2 𝐶𝑝 𝑃2 𝑑𝑃 𝑉
∆Sg = ‫𝑇׬‬1 𝑑𝑇 - R‫𝑃׬‬1 the reservoir = -1mol*8.3145 J/mol-K*(130+273.15)K*ln (𝑉2 )
𝑇 𝑃 1
J 6.5𝑏𝑎𝑟 𝑑𝑃 ∆Sres = ∆Ssurr 2.5
∆Sg = 0 – 8.3145mol−K ‫׬‬2.5 𝑏𝑎𝑟 𝑃 = -1mol*8.3145 J/mol-K*403.15K*ln (6.5)
𝑄𝑠𝑢𝑟𝑟
∆Ssurr = W = 3202.86J/mol
∆Sg = -7.95 J/mol-K 𝑇σ

In 1 mole, ∆Sg = -7.95 J/K Work Reversible Work actual, Wa = 1.3* 3202.86 J/mol
W = - ‫𝑉𝑑𝑃 ׬‬ Wa = 4163.72 J/mol
𝑛𝑅𝑇
=-‫׬‬ 𝑑𝑉
𝑉
 Solution Continuation
Given :
n = 1 mol P2 = 6.5 bar
isothermal
T1 = 1300C T2 = 1300C
Irreversible
P1 = 2.5 bar
T surr = 25oC
Required : ∆Sg, ∆Sres , ∆Stotal

Qa+Wa = ∆U
Wa = 4163.72 J/mol, ∆U at isothermal condition, ideal gas = 0 To get the ∆Stotal
Qa = -Wa (Based on gas as the system)
Qa = - 4163.72 J/mol ∆Ssurr = 13.96 J/K
Qsurr = -Qa = 4163.72J/mol ∆Sg = -7.95 J/K

4163.73𝐽/𝑚𝑜𝑙 ∆Stotal = 6.01 J/K

∆Ssurr = 298.15𝐾

∆Ssurr = 13.96J/mol-K, or just 13.96 J/K

Practice Problems
1. A rigid vessel of 0.06 m3 volume contains an ideal gas, CV = (5/2)R, at 500 K and 1 bar.

(a) If heat in the amount of 15,000 J is transferred to the gas, determine its entropy change.
(Ans. 20.794J/K)

(b) If the vessel is fitted with a stirrer that is rotated by a shaft so that work in the amount of 15,000 J is done
on the gas, what is the entropy change of the gas if the process is adiabatic? What is ΔStotal? Is the process
reversible?
(Ans. ΔS gas = 20.794J/K, ΔS surr = 0, ΔS sys = 20.794J/K)
Entropy Balance and the concept of lost Work
Entropy Balance and the concept of lost Work
Sample Problem
A steady-flow adiabatic turbine (expander) accepts gas at conditions T1, P1, and
discharges at conditions T2, P2. Assuming ideal gase, determine Ws, Wideal, Wlost, and
SG for one the following,. Take Tσ = 300 K.
T1 = 500 K, P1 = 6 bar, T2 = 371 K, P2 = 1.2 bar, Cp/R = 7/2.
 Solution

Required : Ws, Wideal, Wlost, and SG

Wideal = Δ(H)fs  −  Tσ*Δ(S)fs
To compute for shaft work, Ws: Wideal = -3754.0 J/mol – 300K* 4.698 J/mol-K
To get ideal Work
Wideal = -5163.4 J/mol
Q+Ws = ∆H Wideal = Δ(H)fs  −  Tσ*Δ(S)fs
To find the lost Work,
Q = 0, therefore Ws = ∆H ∆Sfs=∆S Wlost = 𝑊𝑖𝑑𝑒𝑎𝑙 − 𝑊𝑠
∆H = Cp(T2 – T1) Δ(H)fs  = ∆H Wlost = 1409.4 J/mol
∆H = 7/2 * 8.3145 J/mol-K * (371-500)K 𝑇2 𝐶𝑝 𝑃2 𝑑𝑃
Since the gas is ideal, ∆S = ‫𝑇׬‬1 𝑑𝑇 - R‫𝑃׬‬1 To get entropy generation, Sg
𝑇 𝑃
∆H = -3754.0 J/mol 371𝐾 𝐶𝑝 1.2 𝑑𝑃 Wlost = Tσ*Sg
∆S = ‫׬‬500𝐾 𝑑𝑇 - R‫׬‬6
Ws = -3754.0 J/mol 𝑇 𝑃 1409.4 J/mol = 300K*Sg
∆S = 4.698 J/mol-K Sg = 4.698 J/mol-K
Practice Problems
Repeat the previous problem for T1 = 450 K, P1 = 5 bar, T2 = 376 K,
P2 = 2 bar, CP/R = 4.

(Ans.-2460.9J/mol, -2953.9J/mol, 493J/mol, 1.643J/mol-K, resp)

Thermodynamic Flow Processes
• Common Flow Processes
• Flow in Ducts / Nozzles
• Fluid Expansion in Turbines
• Fluid Compression / Pumping
• Throttling Process
Expansion in Turbine
Fluid Compression
Fluid Pumping

If V is independent of P:

If V is dependent of P :

Where β is the volume expansivity

Throttling Process
• When a fluid flows through a restriction,
such as an orifice, a partly closed valve,
or a porous plug, without any
appreciable change in kinetic or
potential energy, the primary result of
the process is a pressure drop in the
fluid. Such a throttling process produces
no shaft work, and in the absence of
heat transfer, the energy balance
reduces to
Rankine Cycle

𝑊𝑛𝑒𝑡 𝑊𝑡+𝑊𝑝
ƞ = =
𝑄ℎ 𝑄ℎ
Sample Problem
A simple ideal Rankine cycle operates such that the condenser
produces saturated water at 70C. Water is compressed to 5MPa
and heated in the boiler to produce saturated steam. Assume
pump and turbine to operate isentropically.
A. Quality of steam produced from the turbine
B. Thermal efficiency of the cycle
C. Flow Rate of Steam required to produce 500kW net
power using this cycle
D. If the thermal efficiency of the cycle is 25%, calculate the
steam quality leaving the turbine.
Use the data below
T (oC) P(kPa) Enthalpy (kJ/kg) Entropy (kJ/kg-K)
Liquid Vapor Liquid Vapor
Compressed
70 5000 297.16 ---- 0.9505 ----
80 5000 338.95 ---- 1.0723 ----
Saturated
70 31.19 292.98 2626.8 0.9549 7.7553
80 47.39 334.91 2643.7 1.0753 7.6122
263.99 5000 1154.2 2794.3 2.9202 5.9734
3
Solution to part a
T (oC) P(kPa) Enthalpy (kJ/kg) Entropy (kJ/kg-K)
Liquid Vapor Liquid Vapor
Compressed
70 5000 297.16 ---- 0.9505 ----

80 5000 338.95 ---- 1.0723 ----

Saturated
70 31.19 292.98 2626.8 0.9549 7.7553

80 47.39 334.91 2643.7 1.0753 7.6122

263.99 5000 1154.23 2794.3 2.9202 5.9734

Required : Steam quality, x

Step 1-2, Isentropic Expansion of Turbine Using x’ = 0.7379 , find H’2 via interpolation at 31.19kPa, satd
@ P1 = 5MPa (satd) H1 = 2794.3 kJ/kg, S1 = 5.9734 kJ/kg-K x H
S1 = S’2 = 5.9734 kJ/kg-K
0 292.98
Interpolating at 31.19kPa, satd condition
1 2626.8
S x
@x’ = 0.7379 , H’2= 2015.11 kJ/kg,
0.9549 0
∆H12 = ƞt ∆H’12 , for isentropic turbine, ƞt = 1
7.7553 1
∆H12 = 1*(H’2 – H1) = 1*(2015.11-2794.3)kJ/kg
@S’2= 5.9734 kJ/kg-K, x’ = 0.7379 ∆H12 = -779.19kJ/kg
T (oC) P(kPa) Enthalpy (kJ/kg) Entropy (kJ/kg-K)
Liquid Vapor Liquid Vapor
Compressed
70 5000 297.16 ---- 0.9505 ----

80 5000 338.95 ---- 1.0723 ----

Saturated
70 31.19 292.98 2626.8 0.9549 7.7553

80 47.39 334.91 2643.7 1.0753 7.6122

263.99 5000 1154.23 2794.3 2.9202 5.9734

Required : Steam quality, x

∆H12 = -779.19kJ/kg
∆H12 = H2 – H1→ -779.19 = H2 – 2794.3 To find the actual entropy at second condition, S2.
H2 = 2015.11 kJ/kg , Actual H2 Use x to interpolate at 31.19kPa, satd condition
Use this H2 to find the actual vapor quality, x. x S
@x= 0.7379,
Interpolate at 31.19kPa, satd condition 0 0.9549
S2 = 5.973 kJ/kg-K
H x 1 7.7553

292.98 0 @H2= 2015.11 kJ/kg,

If ƞt is less than 1, actual properties, (x, H2 and S2) will be different from
2626.8 1 x = 0.7379 isentropic properties (x’, H’2 and S’2)
T (oC) P(kPa) Enthalpy (kJ/kg) Entropy (kJ/kg-K)
Liquid Vapor Liquid Vapor
Compressed
70 5000 297.16 ---- 0.9505 ----

80 5000 338.95 ---- 1.0723 ----

Saturated
70 31.19 292.98 2626.8 0.9549 7.7553

80 47.39 334.91 2643.7 1.0753 7.6122

263.99 5000 1154.23 2794.3 2.9202 5.9734

Required : Cycle efficiency, ƞc

To find the ƞc
ƞc =
𝑊𝑛𝑒𝑡
=
𝑊𝑡+𝑊𝑝
To compute for the actual Pump work Wp Wp = H4 - H3
𝑄ℎ 𝑄ℎ
5.16756 kJ/kg = H4 - 292.98 kJ/kg
Actual work of turbine, Wt Wp = W’p /ƞp, when pump is isentropic, ƞp = 1 H4 = 298.1475 kJ/kg
Wt = ƞt (W’t ) or Wt = ƞt (∆H’12 ) or Wt = ∆H12
Wp = 5.16756 kJ/kg Then Qh = H1 - H4
Wt = ∆H12 = -779.19kJ/kg Qh = (2794.3 - 298.1475) kJ/kg
Isentropic work of pump W’p = V (∆P) To get Qh
Qh = 2496.15 kJ/kg
W’p = V (P4- P3) Qh = ∆H14 = H1 – H4 ƞc =
𝑊𝑛𝑒𝑡
=
𝑊𝑡+𝑊𝑝
=
𝑊𝑡+𝑊𝑝
V is the specific volume @ 700C, satd liquid 𝑄ℎ 𝑄ℎ 𝑄ℎ
To get H4, Wp = H4 - H3 ƞc = 0.31
W’p = 1.04 x10^-3 m3/kg (5000- 31.19)kPa
W’p = 5.16756 kJ/kg
To get H3 use H at 700C, satd liquid, then H3 = 292.98 kJ/kg
Required : Flow Rate of Steam required to produce 500kW net power
: Quality of steam X2 at thermal efficiency of 25%

To find the 𝑚ሶ
𝑊ሶ net = 𝑚ሶ 𝑊𝑛𝑒𝑡
500 kW = 𝑚ሶ 𝑊𝑡 + 𝑊𝑝
500kW = -𝑚ሶ *(-779.19 + 5.16756) kJ/kg
𝑚ሶ = 0.65 kg/s

If the thermal efficiency ƞc is just 25% Interpolation at 31.19kPa, satd

ƞc =
𝑊𝑛𝑒𝑡
=
𝑊𝑡+𝑊𝑝 condition
𝑄ℎ 𝑄ℎ
H x
𝐻2 −2794.3 +(298.15−292.98)
0.25 = 292.98 0
𝑄ℎ
2626.8 1
(𝐻2 −2794.3)+5.17
0.25 = ( ) * -1
2496.15
@H2= 2165.09 kJ/kg,
H2 = 2165.09 kJ/kg x = 0.80
Practice Problems
Steam enters the turbine of a power plant operating on the Rankine
cycle at 873.15 K (600°C) and exhausts at 30 kPa. To show the effect of
boiler pressure on the performance of the cycle, calculate the thermal
efficiency of the cycle and the quality of the exhaust steam from the
turbine for boiler pressures of 5000kPa. Assume isentropic turbine and
pump
Ans. x = 0.925, n = 0.359
Gas Power Cycles
• Otto Cycle
• Diesel Cycle
• Brayton Cycle
• Ericsson-Stirling Cycle
Otto Cycle / Ideal Cycle for Spark Ignition
Engine
• An Otto cycle is an idealized thermodynamic cycle that describes the
functioning of a typical spark ignition piston engine. It is the
thermodynamic cycle most commonly found in automobile engines.

• The four-stroke engine was first patented by Alphonse Beau de

Rochas in 1861. Before, in about 1854–57, two Italians (Eugenio
Barsanti and Felice Matteucci) invented an engine that was rumored
to be very similar, but the patent was lost.

• The first person to build a working four-stroke engine, a stationary

engine using a coal gas-air mixture for fuel (a gas engine), was
German engineer Nicolaus Otto. This is why the four-stroke principle
today is commonly known as the Otto cycle and four-stroke engines
using spark plugs often are called Otto engines.
Stages of an Otto Cycle
Equations for Otto Cycle

𝑊𝑛𝑒𝑡 𝑊34+𝑊12
MEP = 𝑉𝑚𝑎𝑥−𝑉𝑚𝑖𝑛 = 𝑉1−𝑉2
Diesel Engine / Ideal Cycle for Spark Ignition
Engine
• Diesel engines operate on a cycle similar to the Otto cycle, but
they do not employ a spark plug.

• The compression ratio for a diesel engine is much greater

than that for a gasoline engine.

• Air in the cylinder is compressed to a very small volume, and as

a consequence, the cylinder temperature at the end of the
compression stroke is very high.

• Diesel engines are more efficient than gasoline engines

because of their greater compression ratios and resulting
higher combustion temperatures.
Equations for Diesel Cycle
•;

𝑊𝑛𝑒𝑡 𝑊34+𝑊12+𝑊34
MEP = 𝑉𝑚𝑎𝑥−𝑉𝑚𝑖𝑛 = 𝑉1−𝑉2
 Stirling and Ericcson Cycle
Stirling Cycle Ericcson Cycle

Qin Qin

Qout
Qout

𝑊𝑛𝑒𝑡
MEP = 𝑉𝑚𝑎𝑥−𝑉𝑚𝑖𝑛

The main advantage of the Ericsson cycle over the Carnot cycle and the Stirling Cycle is, it maintains the smaller pressure ratio for the given ratio of
maximum to minimum specific volume with the higher Mean Effective pressure.
Brayton Cycle / Ideal cycle for gas-turbine
engine

Where TR or temparature ratio = Tb / Ta

And PR is the pressure ratio = Pb/Pa

Options for operating Brayton cycle gas turbine engines

𝑊𝑐
𝑏𝑎𝑐𝑘𝑤𝑜𝑟𝑘 𝑟𝑎𝑡𝑖𝑜 =
𝑊𝑡
Sample Problem
One kg of air at 101.35kPa, 210C is
compressed in an Otto cycle with a
compression ratio of 7 to 1. During the
combustion process, 953.66kJ of heat is
added to the air.
a. Compute the specific volume,
pressure and temperature at four
points in the cycle.
b. Compute also the efficiency and the
MEP. Assume ideality
Solution to part a
Given : n = 1kg air
P1 = 101.35kPa = 101,350kPa
T1 = 294.15K
r=7
Heat added to air, QH = 953.66kJ

Required : P V, T at each point

@ Step 1-2, Isentropic Compression P1 V1γ = P2 V2γ , where γ =1.4

To get V1, used ideal gas law 101.35 kPa * (0.02413 m3/mol )1.4 = P2 * (3.4471x10-3 m3/mol )1.4
V1 = RT1/P1 P2 = 1545.14 kPa
V1 = 0.02413 m3/mol or 0.8321 m3/kg To get T2, used ideal gas law
V1/ V2 = 7 T2 = P2*V2/R
Thus V2 = 3.4471x10-3 m3/mol or 0.1189 m3/kg T2 = (1545.14 x103 Pa)* 3.4471x10-3 m3/mol /8.3145 J/mol-K
To find P2 use isentropic equation T2 = 640.6 K
Solution to part a
Given : n = 1kg air = 34.48 mol
P1 = 101.35kPa = 101,350kPa
T1 = 294.15K
r=7
Qh = 953.66kJ

Required : P V, T at each point

@ Step 2-3, Constant Volume Heat Addition To get P3, used ideal gas law
Q H + W = ∆U, W = 0 P3 = RT3/V3

QH = ∆U23 P3 = 8.3145 J/mol-K * 1971.2K/3.4471x10-3

P3 = 4754.59kPa
QH = n*Cv*(∆T23)
@ Step 3-4, Isentropic Expansion
953.66x103J = 34.48mol*5/2*8.3145 J/mol-K (T3- 640.6K)
V1 = V4 = 0.02413 m3/mol or 0.8321 m3/kg
T3 = 1971.2K
P3 V3γ = P4 V4γ
At constant V, V2 = V3 = 3.4471x10-3 m3/mol or 0.1189 m3/kg P4 = 311.89kPa
To get T4 use ideal gas law, T4 = 905.15K
Solution to part b
Given : n = 1kg air = 34.48 mol
P1 = 101.35kPa = 101,350kPa
T1 = 294.15K
r=7
Qh= 953.66kJ

Required : MEP

To get MEP
𝑊𝑛𝑒𝑡 𝑊34+𝑊12
Wnet = W34 + W12
MEP = =
𝑉𝑚𝑎𝑥−𝑉𝑚𝑖𝑛 𝑉1−𝑉2 Wnet = 5/2*R*(T4-T3) + 5/2*R*(T2-T1)
𝑊34+𝑊12
MEP = Wnet = 5/2*8.3145*(905.15-1971.2) + 5/2*8.3145*(640.6-294.15)
𝑉1−𝑉2
Isentropic expansion, W34 = ∆U34 Wnet = -14957.79 J/mol
W34 = 5/2*R*(T4-T3) V1 – V2 = (0.02413-3.4471x10-3 )m3/mol
Isentropic compression, W12 = ∆U12 V1 – V2 = 0.0206 m3/mol
W12= 5/2*R*(T2-T1) MEP = 726106.31Pa or 726kPa
Solution to part b
Given : n = 1kg air = 34.48 mol
P1 = 101.35kPa = 101,350kPa
T1 = 294.15K
r=7
Heat added to air = 953.66kJ

Required : efficiency

To get efficiency
Ƞ = 1-r1-γ = 1-71-1.4
Ƞ = 0.5408 or 54.08%

𝑊𝑛𝑒𝑡 −14957.79 J/mol

Or Ƞ = = 953.66x103J
𝑄ℎ
34.48 mol
Ƞ = 54.08%
Practice Problem
An ideal Diesel engine uses air initially at 200C and 90kPa at the beginning of the compression process. If the
compression ratio is 15 and the maximum temperature in the cycle is 20000C, determine the following:
A) Net work (812kJ/mol)
B) MEP (930kPa)
C) Cut off ratio (2.6)
Heat Pump and Refrigerators
• In a heat engine, the direction of energy transfer is from the hot reservoir
to the cold reservoir, which is the natural direction. The role of the heat
engine is to process the energy from the hot reservoir so as to do useful
work. What if we wanted to transfer energy from the cold reservoir to the
hot reservoir?

• Because that is not the natural direction of energy transfer, we must put
some energy into a device to be successful. Devices that perform this
task are called heat pumps and refrigerators. For example, homes in
summer are cooled using heat pumps called air conditioners. The air
conditioner transfers energy from the cool room in the home to the
warm air outside.
Clausius Statement of Second Law -
COP and the Effectiveness of a Heat Pump
• The COP is similar to the thermal efficiency for a heat engine in that it is a ratio of what you
gain (energy transferred to or from a reservoir) to what you give (work input).
• For a heat pump operating in the cooling mode, “what you gain” is energy removed from the
cold reservoir.

• The most effective refrigerator or air conditioner is one that removes the greatest amount
of energy from the cold reservoir in exchange for the least amount of work.

• A good refrigerator should have a high COP, typically 5 or 6.

COP and the Effectiveness of a Heat Pump
• In addition to cooling applications, heat pumps are becoming increasingly popular
for heating purposes.
• The energy-absorbing coils for a heat pump are located outside a building, in
contact with the air or buried in the ground. The other set of coils are in the
building’s interior. The circulating fluid flowing through the coils absorbs energy
from the outside and releases it to the interior of the building from the interior
coils.
• In the heating mode, the COP of a heat pump is defined as the ratio of the
energy transferred to the hot reservoir to the work required to transfer that
energy:
Carnot Refrigerator
Refrigeration Cycle – Ideal Vapor Compression
Cycle
Refrigeration Cycle – Ideal Gas Compression
Cycle
Sample Problem
• An Ideal Vapor compression refrigeration cycle operates between
0.1MPa and 0.8MPa uses refrigerant-134A as working fluid. Using the
data below, determine the following:
T (oC) P(MPa) Enthalpy (kJ/kg) Entropy (kJ/kg-K)
Liquid Vapor Liquid Vapor
Saturated
-26.43 0.1 16.29 231.35 0.0678 0.9395
31.33 0.8 93.42 264.15 0.3458 0.9006
Superheated
40 ---- 273.66 ---- 0.9374

50 0.8 ----- 284.39 ----- 0.9711

60 ----- 294.98 ---- 1.034

-Quality of the Vapor from the throttling valve

-COPh
-If the throttling valve is replaced by an expansion turbine, calculate the
COPh of the cycle
Solution to part a
Given : Pmin = 0.1MPa and
Pmax = 0.8MPa
Required : Quality of the Vapor from the
throttling valve

@ Step 1-4 Isenthalpic Flow

H1 = H4;
H4 (satd liquid at 0.8MPa) = 93.42 kJ/kg
To determine the quality of the vapor at point 4,
T (oC) P(MPa) Enthalpy (kJ/kg) Entropy (kJ/kg-K)
Interpolate at 0.1MPa,satd Liquid Vapor Liquid Vapor
H x Saturated
-26.43 0.1 16.29 231.35 0.0678 0.9395
16.29 0 31.33 0.8 93.42 264.15 0.3458 0.9006
Superheated
231.35 1
40 ---- 273.66 ---- 0.9374
@H4 = 93.42 kJ/kg
50 0.8 ----- 284.39 ----- 0.9711
X = 0.36
60 ----- 294.98 ---- 1.034
Solution to part b
Given : Pmin = 0.1MPa and
Pmax = 0.8MPa
Required : COPh
𝑄ℎ
To get COPh., COPh = 𝑊𝑛𝑒𝑡
@ Step 2-3 Compression
P2 = 0.1MPa (satd vapor) H2 = 231.35 kJ/kg
P3 = 0.8MPa (compressed) H3 = 284.39 kJ/kg
Wc = (284.39 - 231.35)kJ/kg T (oC) P(MPa) Enthalpy (kJ/kg) Entropy (kJ/kg-K)
Wc= 53.04kJ/kg Liquid Vapor Liquid Vapor
Saturated
Wnet = Wc = 53.04kJ/kg -26.43 0.1 16.29 231.35 0.0678 0.9395

To get Qh, look condenser unit 31.33 0.8 93.42 264.15 0.3458 0.9006
Superheated
Qh = H 4 – H3 40 ---- 273.66 ---- 0.9374

Qh = (93.42 – 284.39)kJ/kg Qh = -190.97kJ/kg

50 0.8 ----- 284.39 ----- 0.9711
𝑄ℎ 60 ----- 294.98 ---- 1.034
COPh = = 3.6
𝑊𝑛𝑒𝑡
Solution to part c
Given : Pmin = 0.1MPa and
Pmax = 0.8MPa
Required : If the throttling valve is replaced by an expansion
turbine, calculate the COPh of the cycle

𝑄ℎ 𝑄ℎ
COPh = 𝑊𝑛𝑒𝑡 = 𝑊𝑡+𝑊𝑐
@ Step 4-1 Expansion in Turbine, Assume Isentropic
S4 (satd liquid at 0.8MPa) = 0.3458 kJ/kg-K
S4 = S’1 = 0.3458 kJ/kg-K T (oC) P(MPa) Enthalpy (kJ/kg) Entropy (kJ/kg-K)
Use S’1 and interpolate at 0.1MPa, S x Liquid Vapor Liquid Vapor
Saturated
satd to find X’ 0.0678 0
-26.43 0.1 16.29 231.35 0.0678 0.9395

X’ = 0.3189 0.9395 1 31.33 0.8 93.42 264.15 0.3458 0.9006

Superheated
x H 40 ---- 273.66 ---- 0.9374

Use X’ = 0.3189,
0 16.29 50 0.8 ----- 284.39 ----- 0.9711
to find new H’1 60 ----- 294.98 ---- 1.034
1 231.35
Solution to part c
Given : Pmin = 0.1MPa and
Pmax = 0.8MPa
Required : If the throttling valve is replaced by an expansion
turbine, calculate the COPh of the cycle

@ Step 4-1 Expansion in Turbine, Assume Isentropic

H’1 = 84.88 kJ/kg
@ isentropic ƞ = 1 thus H’1 = H1
We can now find the work done by the Turbine
T (oC) P(MPa) Enthalpy (kJ/kg) Entropy (kJ/kg-K)
Wt = H1 – H4 Liquid Vapor Liquid Vapor
Wt = (84.88 - 93.42) kJ/kg Saturated
-26.43 0.1 16.29 231.35 0.0678 0.9395
Wt = -8.54 kJ/kg 31.33 0.8 93.42 264.15 0.3458 0.9006
Superheated
40 ---- 273.66 ---- 0.9374
𝑄ℎ −190.97kJ/kg
COPh = 𝑊𝑡+𝑊𝑐 = 𝑘𝑗 = 4.29
−8.54𝑘𝑔+53𝑘𝐽/𝑘𝑔 50 0.8 ----- 284.39 ----- 0.9711
60 ----- 294.98 ---- 1.034
Practice Problem
There are required 1.2kJ/sec-ton refrigeration for a Carnot refrigerator
to maintain a low temperature region at 250K. If the refrigerator is
producing 4 tons of refrigeration, find the power requirement in hp,
Temperature at the reject Th, COP at low temp, heat rejected Btu/min.
Ans 6.43hp, 335K, 2.94, 1073 BTU/min
References
• Smith, J.M., H.C. Van Ness, M.M. Abbott. Introduction to Chemical Engineering
Thermodynamics, 8th edition. 2018,McGraw Hill
• Serway, R., Jewett, J., Physics for Scientists and Engineers with Modern Physics, 9th Ed.,
2014, Cengage Learning
• Olano, Servillano S.B Jr. et.al, Reviewer for Chemical Engineering Licensure Exam 3rd Ed.,
2012, Manila Review Institute Inc.,
• Kyle, B.G. Chemical and Process Thermodynamics.,3rd edition, 1999, Prentice Hall.
• Roy, B. N. Fundamentals of Classical and Statistical Thermodynamics.2002, John Wiley
• Sandler, S. I. Chemical and Engineering Thermodynamics., 3rd ed., 1999, John Wiley &
Sons., Inc.
• https://extrudesign.com/ericsson-cycle/#google_vignette
• https://web.mit.edu/16.unified/www/SPRING/propulsion/notes/node27.html