MECH 240 - Thermodynamics 1

Chapter 1 - Basic concepts

Introduction:
● 1st law of thermodynamics - Conservation of energy
○ Energy cannot be created or destroyed
○
● 2nd law of thermodynamics - Entropy
○ Determines energy of a process
○ Measure of randomness/disorder
● We take “classical thermodynamics”
○ Macroscopic approach
Units:
● Two systems
○ Metric SI
○ English or US customary (USCS)
● Primary dimensions
○ Time [s]
○ Length [m]
○ Mass [kg]
○ Electric current [A]
○ Temperature [K]
○ Amount [mol]
○ Luminous intensity [cd]
● Secondary dimensions
○ Also called derived dimensions
Basic definitions:
● Parts of a system
○ System
■ Quantity of matter (or area) of interest
○ Surroundings
■ Mass (or area) outside system
○ Boundary
■ Surface between system and surroundings
● Types of systems
○ Isolated system
■ Mass: fixed
■ Energy: fixed
■ Volume: vary
○ Closed system (control mass)
■ Mass: fixed
 ■ Energy: vary
■ Volume: vary
○ Open system (control volume)
■ Mass: vary
■ Energy: vary
■ Volume: vary
● Properties
○ Any characteristic of system
○ Types of properties
■ Intensive properties
● Independent of mass
𝑒𝑥𝑡𝑒𝑛𝑠𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦
● Specific properties: 𝑚𝑎𝑠𝑠
● State (of simple compressible system) is fully defined
by 2 independent intensive properties
○ Absence of external force fields (electrical, gravitational, etc)
■ Extensive properties
● Depend of size
○ Density and Specific volume
𝑚
■ ρ= 𝑉
(density)
𝑉 1
■ 𝑣= 𝑚
= ρ
(specific volume)
■ Functions of temperature (T) and pressure (P)
○ Specific gravity (relative density)
ρ ρ
■ 𝑆𝐺 = ρ𝑤𝑎𝑡𝑒𝑟
= 3
1000 𝑘𝑔/𝑚
○ Specific weight

■
● Equilibrium
○ Thermal: Temperature (T) is uniform
○ Mechanical: Pressure (P) is uniform
○ Phase: Mass doesn’t vary with phase
○ Chemical: No chemical reaction occurs
● Process
○ Change system undergoes
○ Path: series of states system passes through
○ To fully describe process:
■ Initial and final states
■ Path
■ Interactions with surroundings
○ Steady: no change which respect to time
○ Uniform: no change with respect to location
● Types of process
○ Quasi-equilibrium (quasi-static): system is infinitesimally close to equilibrium
 ○ Isothermal: Temperature (T) is constant
○ Isobaric: Pressure (P) is constant
○ Adiabatic: No heat transfer (𝑄 = 0)
○ Isochoric (isometric): Specific volume (v) is constant
○ Cycles: System returns to original state
○ Steady flow: fluid flows through control volume (volume, mass, energy are
constant)
𝑛
○ Polytropic: 𝑃𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 applies
○ Isentropic: Entropy (S) is constant (ie. adiabatic + internally reversible)
Temperature:
● Celsius [oC] / Kelvin [K]
𝑜
○ 𝐾𝑒𝑙𝑣𝑖𝑛 = 𝐶 + 273
● Fahrenheit [oF] / Ranskin [R]
○
𝑜
○ 𝑅𝑎𝑛𝑘𝑖𝑛𝑒 = 𝐹 + 460
Pressure:
● Units
○ SI: [Pa]
5
■ 1 [𝑏𝑎𝑟] = 10 [𝑃𝑎], 1 [𝑎𝑡𝑚] = 1. 01325 [𝑏𝑎𝑟𝑠]
○ USCS: [psi]
■ 1 [𝑎𝑡𝑚] = 14. 696 [𝑝𝑠𝑖]
● Types of pressures
○ Absolute pressure: pressure relative to vacuum
○ Gage pressure (P<Patm)
■ 𝑃𝑔𝑎𝑔𝑒 = 𝑃𝑎𝑏𝑠 − 𝑃𝑎𝑡𝑚
○ Vacuum pressure (P>Patm)
■ 𝑃𝑔𝑎𝑔𝑒 = 𝑃𝑎𝑡𝑚 − 𝑃
𝑎𝑏𝑠
○ note: Always positive quantities
● Pressure increases linearly with depth
○ Since more fluid on top
○
○ Negligible for gases
● Manometer
○ Device to measure pressure
○ ↗P → down, ↘P → up
○ Two equal elevation points have same pressure in same fluid
○ ρ changes when fluid changes
○ P at boundary of substance are equal
● Barometer
○ Device used to measure atmospheric pressure
○ 𝑃𝑎𝑡𝑚 = ρ𝐻𝑔𝑔ℎ, mercury (Hg) is often used
 3
○ ρ𝐻𝑔 = 13595 𝑘𝑔/𝑚
5
○ 1 𝑚𝑚𝐻𝑔 = 1 [𝑡𝑜𝑟𝑟] = 1 [𝑎𝑡𝑚] = 1. 01325 · 10 [𝑃𝑎]

Chapter 2 - General energy analysis

Forms of energy:
● Microscopic forms
○ Molecular activity
○ Independent of reference frame
● Macroscopic forms
○ Kinetic and potential energy
○ Depends on reference frame
● Types of energy
○ Kinetic energy

■
○ Potential energy
■ 𝑃𝐸 = 𝑚𝑔𝑧
○ Internal energy
■ Denoted: U
■ Sensible energy: translation, rotation, vibration, spin
■ Latent energy: phase change
■ Nuclear energy: bonds within nucleus
■ Electric and magnetic dipole energy
● Often we want intensive properties
○ ∴use specific energy

○
● Energy due to flow
○ (mass flow rate)

○ (volume flow rate)

○ (energy flow rate)
𝑃
○ 𝑒𝑚𝑒𝑐ℎ = ρ
(flow energy)

Energy transfer:
● Heat
○ Symbol: Q [J]
○ 𝑞 = 𝑄/𝑚 (heat transfer per unit mass)
○ Rate of heat transfer (aka. power)
■ Denoted
 ■
● Work
○ Any energy that crosses boundary that isn’t heat
○ Symbol: W [J]
○ Specific work: 𝑤 = 𝑊/𝑚 [J/kg]
○ Power:
○ Has magnitude and binary direction (in or out)
○ 𝑊𝑠ℎ𝑎𝑓𝑡 = 2π𝑛𝑇
1 2 2
○ 𝑊𝑠𝑝𝑟𝑖𝑛𝑔 = 2
𝑘(𝑥2 − 𝑥1 )
○ 𝑊𝑏𝑜𝑢𝑛𝑑𝑎𝑟𝑦 = 𝑃 ∆𝑉 (boundary work)
● Path functions
○ Heat and work are NOT properties
○ They are energy transfer mechanism
■ Boundary phenomena
■ Associated with process
● note: Properties are point functions (not path, only depend on state)
● ∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚 = (𝑄𝑖𝑛 − 𝑄𝑜𝑢𝑡) + (𝑊𝑖𝑛 − 𝑊𝑜𝑢𝑡) + (𝐸𝑚𝑎𝑠𝑠, 𝑖𝑛 − 𝐸𝑚𝑎𝑠𝑠, 𝑜𝑢𝑡)

Efficiency:
𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑜𝑢𝑡𝑝𝑢𝑡
● η= 𝑖𝑛𝑝𝑢𝑡
● Efficiencies of systems in parallel can be multiplied
● eg. η𝑡𝑢𝑟𝑏𝑖𝑛𝑒−𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑜𝑟 = η𝑡𝑢𝑟𝑏𝑖𝑛𝑒 · η𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑜𝑟

Chapter 3 - Properties of pure substances

Pure substances:
● Uniform chemical composition
○ Can be in different phases
● States
○ Solid
○ Liquid
○ Gas
Phase change process:
● Compressed liquid → saturated liquid → saturated mixture
→ saturated vapor → superheated vapor
● Both Temperature and pressure effect saturation
● Plotted on T-v diagram (sometimes P-v diagram)
○ ↗T ⇒ ↗v ⇒ ↘ρ (since molecular activity)
○ ↗P ⇒ ↗Tsat (higher curve)
■ Since molecules have more force pushing them down
○ ↗T ⇒ ↗Psat (higher curve)
 ● Latent heat
○ Amount of energy absorbed during phase change
■ Used to break intermolecular bonds
■ Results in flat section of T-v diagram
■ note: Direction independent
○ As ↗T ⇒ ↘latent heat
■ Until critical point where L=0
○ 𝐿 = 𝑢𝑔 − 𝑢𝑓, L is latent heat of vaporization, ug is
internal energy of saturated vapor, uf is internal energy
of saturated liquid
● Saturation dome
○ Figure on right
○ Graphs saturation point by varying pressure
● During phase change only, Psat and Tsat are dependent
○ Table 3-1
○ Otherwise, 𝑃 ≠ 𝑓(𝑇)
■ ∴can be 2 intensive properties to fully define state
● Quality
○ Denoted: x [unitless]
○ Intensive property
○ Ratio of vapor to total by mass
𝑚𝑔
■ 𝑥= 𝑚𝑔+𝑚𝑡

● Tables for properties

○ Water
■ Saturated mixture: A-4 & A-5
■ Superheated vapor: A-6
■ Compressed liquid: A-7
○ r-134a (refrigerant)
■ Saturated mixture: A-11 & A-12
■ Superheated vapor: A-13
○ In absence of data (for compressed liquid)
■ 𝑦 ≈ 𝑦𝑓 @𝑇 property is same as saturated liquid at same temperature

Enthalpy:
● Denoted: h [kJ/kg]
● Measures energy required to go from one state to another
● ℎ = 𝑢 + 𝑃𝑣
○ Internal energy + boundary work
○ Internal energy is due to molecular activity, bonds, etc
○ Boundary work is because
● We use enthalpy because pressure is constant (in real life), NOT volume
○ If we only used Δu, we need constant volume to obey 1st law and not have
leaking boundary
 ● Enthalpy doesn’t change with pressure
○ 𝑑𝐻 = 𝑑𝑈 + 𝑃𝑉
○ 𝑑𝐻 = (𝑑𝑞 − 𝑃𝑑𝑉) + 𝑃𝑑𝑉 + 𝑉𝑑𝑃
○ 𝑑𝐻 = 𝑑𝑞 + 𝑉𝑑𝑃
■ Therefore heat at constant pressure is enthalpy
■ ∴∆𝐻 = 𝑄𝑝

Ideal-gas equation:
● Most gases (at room temperature) have special relation between:
−1
○ Relates 𝑃 ∝ 𝑇 ∝ 𝑣
● 𝑃𝑉 = 𝑚𝑅𝑇 ⇒ 𝑃𝑣 = 𝑅𝑇
○ See table A-2 for R values
𝑅𝑢
■ 𝑅= 𝑀𝑚
where Mm is molar mass, Ru is universal gas constant
○ note: T must be in Kelvin
● Assumptions:
○ Neglects interaction between molecules
○ Low density (low pressure & high temperature)
Compressibility factor (Z):
● Corrects for limitations of ideal gas approximation
● 𝑃𝑣 = 𝑍𝑅𝑇
𝑣𝑎𝑐𝑡𝑢𝑎𝑙 𝑃 𝑣𝑎𝑐𝑡𝑢𝑎𝑙
○ 𝑍= 𝑣𝑖𝑑𝑒𝑎𝑙
= 𝑅𝑇
𝑃 𝑇
○ 𝑃𝑅 = 𝑃𝑐𝑟
(reduced pressure) 𝑇𝑅 = 𝑇𝑐𝑟
(reduced temperature)
○ Z factor for all gasses is same for same PR and TR
■ ∴use PR and TR to find Z using charts
● Generalized compressibility chart
𝑣𝑎𝑐𝑡𝑢𝑎𝑙
○ 𝑣𝑅 = 𝑅𝑇𝑐𝑟 / 𝑃𝑐𝑟

Other models of state:

● Many different equation of state exist to relate P, T, and v but all approximations with
different strengths
○ Van der Waals
■ Accounts for intermolecular forces
■ Accounts for volume occupied by molecules
○ Beattie-Bridgmena
○ Benedict-Webb-Rubin
○ Virial

Chapter 4 - Energy analysis of closed systems

Boundary work:
● If gas expands or contracts, work is done (since system is always under pressure Patm)
 ○ (+)Wb → expansion
○ (-)Wb → compression
● 𝑊𝑏 = ∫𝑃 𝑑𝑉 where P is pressure, 𝑑𝑉 = 𝐴𝑑𝑠
○ ∴area under P-V diagram (given 𝑃 = 𝑓(𝑉))
● Boundary work is path function
○ 𝑊𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑜𝑛 > 𝑊𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑜𝑛
○ Not reversible ⇒ 𝑊𝑛𝑒𝑡 > 0 (during cycle)
● Polytropic process
𝑛
○ 𝑃𝑉 = 𝐶 where n and C are constants
𝑃2 𝑉2−𝑃1 𝑉1
○ 𝑊𝑏 = 1−𝑛
○ For ideal gasses
𝑚𝑅(𝑇2−𝑇1)
■ 𝑊𝑏 = 1−𝑛

Specific heat:
● Energy required to raise 1kg of mass of substance by 1K
● Denoted: c [kJ/Kg⋅oC]
● Specific heat at constant volume (cv)
∂𝑢
○ 𝑐𝑣 = ( ∂𝑇 )𝑣
○ Assumes constant volume
● Specific heat at constant pressure (cp)
∂ℎ
○ 𝑐𝑝 = ( ∂𝑇 )𝑝
○ Assumes constant pressure
● 𝑐𝑝 > 𝑐𝑣
For ideal gasses:
● Internal energy (u) ⇒ enthalpy (h) ⇒ specific heat (c) → 𝑓(𝑇) (temperature)
○ Smooth variation of cv and cp with temperature
■ ∆𝑢 = ∫𝑐𝑣(𝑇) 𝑑𝑇
■ ∆ℎ = ∫𝑐𝑝(𝑇) 𝑑𝑇
○ note: c is constant for monatomic gasses
● Can approximate as linear over small ΔT
○ ∆𝑢 = 𝑐𝑣, 𝑎𝑣𝑔 ∆𝑇
○ ∆ℎ = 𝑐𝑝, 𝑎𝑣𝑔 ∆𝑇
○ Table A-2b for 𝑐𝑣(𝑇) & 𝑐𝑝(𝑇)
𝑇1+ 𝑇2
■ Use 𝑇𝑎𝑣𝑔 = 2
○ OR use table A-17 directly since 𝑢(𝑇) & ℎ(𝑇)
● Specific heats relation
○ 𝑐𝑝 − 𝑐𝑣 = 𝑅 [J/kg⋅K] where R is ideal gas constant for substance
 ● Specific heat ratio
○ Relates 𝑐𝑣 and 𝑐𝑝
𝑐𝑝
○ 𝑘= 𝑐𝑣
(BUT k varies with temperature since 𝑐(𝑇))

○ 𝑘 ≈ 1. 667 for monatomic gasses

○ 𝑘 ≈ 1. 4 for diatomic gases at room temperature
Solid and liquid properties:
● Solids and liquids are treated as incompressible
○ ∴ v and ρ are constant
○ 𝑊𝑏 = 0
○ 𝑐𝑣 = 𝑐𝑝 = 𝑐
○ 𝑐(𝑇) still function of temperature
■ Table A-3
● Enthalpy
○ ∆ℎ = 𝑐𝑎𝑣𝑔∆𝑇 + 𝑣 ∆𝑃
○ Solids:
■ ∆ℎ = ∆𝑢 = 𝑐𝑎𝑣𝑔∆𝑇 (constant pressure)
○ Liquids:
■ ∆ℎ = ∆𝑢 = 𝑐𝑎𝑣𝑔∆𝑇 (constant pressure)
■ ∆ℎ = ∆𝑢 = 𝑣 ∆𝑃 (constant temperature)

Chapter 5 - Mass and energy analysis for control volumes

Conservation of mass:
● Mass cannot be created or destroyed during a process

●
● Assume uniform density over cross section and in terms of average velocity
○
○

● If incompressible liquid or solid:

● Flow work:
○ 𝑤𝑓𝑙𝑜𝑤 = 𝑃𝑣
● Total energy of flowing fluid:
○ Denoted θ
○ θ = 𝑃𝑣 + 𝑒 where e is internal energy
○ θ = 𝑃𝑣 + (𝑢 + 𝑘𝑒 + 𝑝𝑒)
 ○ (since ℎ = 𝑃𝑣 + 𝑢)
○ ∴𝐸 = 𝑚θ
Analysis of steady-flow systems:
● Volume is constant ⇒ 𝑊𝑏 = 0

● Conservation of mass:
● Conservation of energy:
○

○
Steady flow engineering devices:
● Only one inlet and outlet
● Nozzles and diffusers
○ Nozzles: increase velocity of fluid
○ Diffusers: decrease velocity of fluid
○ Assumptions
■ 𝑄≈0
■ 𝑊=0
■ ∆𝑃𝐸 ≈ 0
● Turbines and compressors
○ Turbines: produces electricity (work extracted from system)
○ Compressors: increases pressure of fluid (word supplied to system)
○ Assumptions:
■ 𝑄≈0
■ ∆𝑃𝐸 ≈ 0
■ ∆𝐾𝐸 ≈ 0
● Throttling valve
○ Flow restricting device ⇒ decreases pressure of fluid
○ Isenthalpic device: enthalpy (h) is constant ⇒ ℎ1 = ℎ2
■ Therefore for ideal gas, temperature is constant
○ Assumptions
■ 𝑄≈0
■ 𝑊=0
■ ∆𝑃𝐸 ≈ 0
■ ∆𝐾𝐸 ≈ 0
● Mixing chambers
○ Device that mixes fluid streams
○ Assumptions
■ 𝑄≈0
■ 𝑊=0
■ ∆𝑃𝐸 ≈ 0
 ■ ∆𝐾𝐸 ≈ 0
● Heat exchangers
○ Device where heat exchange but not mixing occurs (for 2 moving fluids)
○ Assumptions
■ 𝑊=0
■ ∆𝑃𝐸 ≈ 0
■ ∆𝐾𝐸 ≈ 0
● Pipe and duct flow
○ Any device allowing transport of liquids and gasses
○ Assumptions
■ ∆𝑃𝐸 ≈ 0
■ ∆𝐾𝐸 ≈ 0
Unsteady flow engineering devices:
● Also called “transient flow” devices
○ Properties change with time
○ Assume inlet/outlet flow doesn’t change with time
● Analysis is like closed system except mass isn’t constant
○ ∆𝑚 = 𝑚2 − 𝑚1 ≠ 0

●
○ note: Boundary work (Wb) is work out

Chapter 6 - Second Law of Thermodynamics

● First law doesn’t guarantee process occurring or direction of process
● 2nd law - entropy
○ Processes occur in certain directions
○ Energy has quality
○ Gives theoretical limits of efficiency (of engineering processes)
Heat engines:
● 𝑇ℎ𝑒𝑟𝑚𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦 [𝐽/𝐾] = 𝑚𝑎𝑠𝑠 [𝑘𝑔] * 𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 ℎ𝑒𝑎𝑡 𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑦 (𝐶) [𝐽/𝑘𝑔. 𝐾]
○ Units: [J/K]
● Assume thermal reservoirs
○ def: Body with large thermal capacity
○ Temperature doesn’t change
○ Supplies constant heat to system
○ Source: reservoir supplying heat (TH)
○ Sink: reservoir absorbing heat (TL)
● Work → heat
○ Natural process (no work required)
● Heat → work
○ Required heat engine
Heat engine:
● Converts heat into work
● Collection of engineering devices
○ Treated as black box
● Boiler (Qin) → turbine (Wout) → condenser (Qout) → pump (Win)
○ Qout is wasted energy (always >0)
○ Kelvin-Planck statement: Impossible to convert all heat into work
● Theoretical thermal efficiency
𝑊𝑛𝑒𝑡, 𝑜𝑢𝑡 𝑄𝐻−𝑄𝐿 𝑄𝐿
○ η𝑡ℎ = 𝑄𝑖𝑛
= 𝑄𝐻
=1− 𝑄𝐻

Refrigerators & heat pumps:

● Refrigerators and heat pumps operate on same process
○ Refrigerators cool cold space
■ QL matters
○ Heat pumps warm hot spaces
■ QH matters
● Transfer heat from low to high (ie. cooling)
○ Requires energy (Win)
○ Usually used refrigerant fluid
● Evaporator (Qin) → compressor (Win) → condenser (Qout) → expansion valve
● Energy balance: 𝑊𝑛𝑒𝑡, 𝑖𝑛 = 𝑄𝐻 − 𝑄𝐿
● Coefficient of performance (COP):
𝑑𝑒𝑠𝑖𝑟𝑒𝑑 𝑜𝑢𝑡𝑝𝑢𝑡
○ 𝐶𝑂𝑃 = 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 𝑖𝑛𝑝𝑢𝑡
𝑄𝐿 𝑄𝐿 1
○ 𝐶𝑂𝑃𝑅𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑡𝑜𝑟 = 𝑊𝑛𝑒𝑡, 𝑖𝑛
= 𝑄𝐻−𝑄𝐿
= 𝑄𝐻/𝑄𝐿−1
𝑄𝐻 𝑄𝐻 1
○ 𝐶𝑂𝑃𝐻𝑒𝑎𝑡 𝑃𝑢𝑚𝑝 = 𝑊𝑛𝑒𝑡, 𝑖𝑛
= 𝑄𝐻−𝑄𝐿
= 1−𝑄𝐿/𝑄𝐻

○ 𝐶𝑂𝑃𝐻𝑃 = 1 + 𝐶𝑂𝑃𝑅
● Clausius statement
○ Heat transfer from low to high requires input energy
■ ∴has effect on surroundings
○ Kelvin-Planck and Clausius statement are equivalent
Reversibility of processes:
● Perpetual motion
○ Perpetual motion machine 1 (PPM1)
■ Device that creates energy
■ Violates 1st law of thermodynamics
○ Perpetual motion machine 2 (PPM2)
■ Device that doesn’t reject heat
■ Violates 2nd law of thermodynamics
● Reversible process
○ Can be reversed without any external effects
 ○ Idealization → usually not possible due to
■ Friction, heat transfer, expansion, mixing, electric resistance, inelastic
deformation, chemical reactions
○ Basis for 2nd law efficiency
● 3 types of reversible processes
○ Totally reversible
■ No irreversibilities in or out of boundary
○ Internally reversible
■ No irreversibilities inside of boundary
○ Externally reversible
■ No irreversibilities outside of boundary
Carnot cycle:
● Theoretical most efficient cycle/process
○ No irreversibilities (∴loss of energy)
● For heat engines
○ 2 isothermal process (T constant)
○ 2 adiabatic process (no heat transfer )
Carnot heat engine:
● Process 1 - Isothermal expansion
○ T constant (at TH)
○ Slow expansion
■ Causes heat transfer in (QH) from source
● Process 2 - Adiabatic expansion
○No heat transfer
○Slow expansion
■ Causes temperature to drop (to TL)
● Process 3 - Isothermal compression
○ T constant (at TL)
○ Slow compression
■ Causes heat transfer out (QL) to sink
● Process 4 - Adiabatic compression
○ No heat transfer
○ Slow compression
■ Causes temperature to rise (to TH)
● note: The reverse is refrigeration cycle
Carnot efficiency:
● Only depends on temperature difference of reservoirs
𝑄𝐻 𝑇𝐻
● 𝑄𝐿
= 𝑇𝐿
for T is Kelvin (or Rankine)

𝑊𝑛𝑒𝑡, 𝑜𝑢𝑡 𝑄𝐻−𝑄𝐿 𝑄𝐿 𝑇𝐿

○ ∴ η𝑡ℎ = 𝑄𝑖𝑛
= 𝑄𝐻
=1− 𝑄𝐻
=1− 𝑇𝐻
 𝑄𝐿 𝑄𝐿 1 1
○ ∴ 𝐶𝑂𝑃𝑅𝑒𝑓𝑟𝑖𝑔𝑒𝑟𝑎𝑡𝑜𝑟 = 𝑊𝑛𝑒𝑡, 𝑖𝑛
= 𝑄𝐻−𝑄𝐿
= 1−𝑄𝐻/𝑄𝐿
= 1−𝑇𝐻/𝑇𝐿
𝑄𝐻 𝑄𝐻 1 1
○ ∴ 𝐶𝑂𝑃𝐻𝑒𝑎𝑡 𝑃𝑢𝑚𝑝 = 𝑊𝑛𝑒𝑡, 𝑖𝑛
= 𝑄𝐻−𝑄𝐿
= 1−𝑄𝐿/𝑄𝐻
= 1−𝑇𝐿/𝑇𝐻

Chapter 7 - Entropy
Clausius inequality:

● where T is temperature at boundary

○ From 2nd law
● Reversible process, integral = 0
Entropy:
● Property of a system/state
○ Units: [kJ/kg⋅K]
○ BUT Sgen is not a property (depends on process path)
● Entropy can not be destroyed but can be created (Sgen)

● where ΔS is change in entropy

● Assuming constant temperature T
𝑄𝑛𝑒𝑡, 𝑖𝑛
○ ∆𝑆 = 𝑇𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

○ Heat transfer in → +ΔS

○ Heat transfer out → -ΔS
● Entropy is generated from irreversible processes
1
● ∆𝑆 = ∫ 𝑇
δ𝑄 + 𝑆𝑔𝑒𝑛 where Sgenerated ≥ 0
○ Sgen depends on process
● Entropy of isolated system increases or remains constant in reversible process
○ ∆𝑆𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 ≥ 0
● Key points
○ Processes occur in one direction 𝑆𝑔𝑒𝑛 ≥ 0
○ Entropy is non-conservative ∆𝑆𝑖𝑠𝑜𝑙𝑎𝑡𝑒𝑑 ≥ 0
○ Entropy measures irreversibilities
● Measures randomness/disorder
Microscopic definition of entropy:
● Boltzmann relation
○ 𝑆 = 𝑘 𝑙𝑛(𝑝)
−23
■ k is Boltzmann constant 𝑘 = 1. 381 · 10 [𝐽/𝐾]
■ p is thermodynamic probability (#of possible microstates for macrostate)
○ ↗disorder → ↗microstates → ↗entropy
○ note: no irreversibilities ⇒ no increase in disorder (internal energy is disordered)
 ● 3rd law of thermodynamics
○ Entropy of pure crystalline substance at absolute zero is zero
■ 𝑆𝑝𝑢𝑟𝑒 𝑐𝑟𝑦𝑠𝑡𝑎𝑙𝑙𝑖𝑛𝑒 @𝐾=0 = 0

Entropy in pure substances:

● Found using tables
● Isentropic means adiabatic + internally reversible
○ S is constant ∆𝑆 = 0
● Graphed in h-s diagrams
● Graphed on T-s diagrams
○ Area under curve is heat transfer for internally reversible
■ Area under curve =
■ If adiabatic, no heat transfer → no temperature change → no area under
curve (straight horizontal line) → ∆𝑆 = 0
○ 𝑇𝑑𝑠 = 𝑑𝑢 + 𝑃𝑑𝑣 (Gibbs equation)
○ 𝑇𝑑𝑠 = 𝑑ℎ − 𝑣𝑑𝑃 (2nd Tds relation)
Entropy for liquids & solids:
● Approximated as incompressible 𝑑𝑣 ≈ 0
● recall: ∆𝑢 = 𝑐 ∆𝑇 for incompressible
𝑇 𝐽
● ⇒ ∆𝑠 ≈ 𝑐𝑎𝑣𝑔 𝑙𝑛( 𝑇2 ) [ 𝑘𝑔·𝐾 ]
1

● Isentropic relation
○ Isentropic incompressible ⇒ isothermal
○ ∆𝑠 = 0
■ T1=T2, ln(1)=0
Entropy for ideal gas:
● recall: 𝑑𝑢 = 𝑐𝑣(𝑇) 𝑑𝑇, 𝑐𝑣 = 𝑐𝑝 − 𝑅 & 𝑃𝑣 = 𝑅𝑇
● Method 1: using average specific heat capacity (cavg)
𝑇 𝑣
○ ⇒ ∆𝑠 = 𝑐𝑣, 𝑎𝑣𝑔 𝑙𝑛( 𝑇2 ) + 𝑅 𝑙𝑛( 𝑣2 ) (Gibbs equation)
1 1
𝑇 𝑃
○ ⇒ ∆𝑠 = 𝑐𝑝, 𝑎𝑣𝑔 𝑙𝑛( 𝑇2 ) − 𝑅 𝑙𝑛( 𝑃2 ) (2nd Tds relation)
1 1

● Method 2: using tables

○ Gives exact values
𝑇
+ 1 + +
■ 𝑠 =∫ 𝑐𝑣(𝑇) 𝑇
𝑑𝑇 ∴ ∆𝑠 = 𝑠 2
−𝑠 1
0
𝑇
𝑜 1 𝑜 𝑜
■ 𝑠 = ∫ 𝑐𝑝(𝑇) 𝑇
𝑑𝑇 ∴ ∆𝑠 = 𝑠 2
−𝑠 1
0
+ 𝑜
■ note: 𝑠 = 𝑠 − 𝑅 𝑙𝑛(𝑇)
○ Table A-17
 + + 𝑣
○ ∆𝑠 = (𝑠 2
− 𝑠 1) + 𝑅 𝑙𝑛( 𝑣2 ) (Gibbs equation)
1

𝑜 𝑜 𝑃
○ ∆𝑠 = (𝑠 2
− 𝑠 1) − 𝑅 𝑙𝑛( 𝑃2 ) (2nd Tds relation)
1

● Isentropic relation (for ideal gas) (∆𝑠 = 0)

○ Assumes constant/avg specific heat (cp and cv)
○ 1st form (no real changes)
𝑇 𝑣
■ (∆𝑠 =) 0 = 𝑐𝑣, 𝑎𝑣𝑔 𝑙𝑛( 𝑇2 ) + 𝑅 𝑙𝑛( 𝑣2 ) (Gibbs equation)
1 1
𝑇2 𝑃2
■ (∆𝑠 =) 0 = 𝑐𝑝, 𝑎𝑣𝑔 𝑙𝑛( 𝑇 ) − 𝑅 𝑙𝑛( 𝑃 ) (2nd Tds relation)
1 1

■ recall: 𝑅 = 𝑐𝑝 − 𝑐𝑣 (ideal gas constant)

○ 2nd form
𝑇2 𝑣 𝑘−1 𝑐𝑝
■ 𝑇1
= ( 𝑣1 ) where 𝑘 = 𝑐𝑣
2
𝑇2 𝑃2 (𝑘−1)/𝑘
■ 𝑇1
=( 𝑃1
)
𝑃2 𝑣 𝑘
■ 𝑃1
= ( 𝑣1 )
2

○ 3rd form (DON’T USE)

𝑘−1
■ 𝑇𝑣 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
(1−𝑘)/𝑘
■ 𝑇𝑃 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑘
■ 𝑃𝑣 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

Chapter 8 - Entropy Analysis

Reversible steady-flow devices:
● Relate work to fluid properties (in steady-flow devices)
● Energy balance:
○ 𝑞𝑛𝑒𝑡 𝑖𝑛 + 𝑤𝑟𝑒𝑣, 𝑛𝑒𝑡 𝑖𝑛 = ∆ℎ + ∆𝑘𝑒 + ∆𝑝𝑒
○ ∆ℎ − ∫𝑣 𝑑𝑃 − 𝑤𝑟𝑒𝑣 = ∆ℎ + ∆𝑘𝑒 + ∆𝑝𝑒 since 𝑞𝑛𝑒𝑡, 𝑖𝑛 = ∆𝑠 = ∆ℎ − 𝑊𝑏
○ 𝑤𝑛𝑒𝑡, 𝑖𝑛 = ∫𝑣 𝑑𝑃 + ∆𝑘𝑒 + ∆𝑝𝑒 [J/kg]
○ 𝑤𝑛𝑒𝑡, 𝑜𝑢𝑡 =− ∫𝑣 𝑑𝑃 − ∆𝑘𝑒 − ∆𝑝𝑒 [J/kg]
○ Conclusions
■ ↗v (↘ρ) → ↗work out (desired in heat engine configuration)
● For incompressible fluid
○ v is constant
○ 𝑤𝑛𝑒𝑡 𝑖𝑛 = 𝑣 ∆𝑃 + ∆𝑘𝑒 + ∆𝑝𝑒 [J/kg]
■ No work interaction → Bernoulli equation
Compressor work:
● Minimal when process is internally reversible
 ● 𝑤𝑛𝑒𝑡, 𝑖𝑛 = ∫𝑣 𝑑𝑃 + ∆𝑘𝑒 + ∆𝑝𝑒 [J/kg] 𝑘𝑒 = 𝑝𝑒 ≈ 0
● 𝑤𝑛𝑒𝑡, 𝑖𝑛 = ∫𝑣 𝑑𝑃
● Minimize work in (required work)
○ Minimize irreversibilities
○ Keep specific volume low (ie. high density) ⇒ low temperature
■ Cool gas during compression process
Isentropic efficiencies for steady flow devices:
● Real systems are not fully reversible
○ Quantify irreversibilities by comparing system to ideal reversible system
● All equations assume 𝑠𝑜 = 0
● Turbines:
𝑎𝑐𝑡𝑢𝑎𝑙 𝑡𝑢𝑟𝑏𝑖𝑛𝑒 𝑤𝑜𝑟𝑘 𝑤𝑎
○ η= 𝑖𝑠𝑒𝑛𝑡𝑟𝑜𝑝𝑖𝑐 𝑡𝑢𝑟𝑏𝑖𝑛𝑒 𝑤𝑜𝑟𝑘
= 𝑤𝑠
(called isentropic efficiency)

○ 𝑤𝑛𝑒𝑡, 𝑖𝑛 = ∫𝑣 𝑑𝑃 = ∆ℎ − ∆𝑠
ℎ1−ℎ2𝑎
○ η𝑇𝑢𝑟𝑏𝑖𝑛𝑒 = ℎ1−ℎ2𝑠

● Compressors and pumps

ℎ2𝑠−ℎ1
○ η𝐶𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑜𝑟 = ℎ2𝑎−ℎ1
𝑤𝑠 𝑣(𝑃2−𝑃1)
○ η𝑃𝑢𝑚𝑝 = 𝑤𝑎
= ℎ2𝑎−ℎ1
(for incompressible fluid)
● Nozzles
○ Assumes (initial velocity)
ℎ1−ℎ2𝑎
○ η𝑁𝑜𝑧𝑧𝑙𝑒 = ℎ1−ℎ2𝑠

○ (no assumption / actual process)

○ (assumes isentropic process)

Entropy balance:
● Usually simpler than energy balance
● ∆𝑆𝑠𝑦𝑠(= 𝑆2 − 𝑆1) = 𝑆𝑖𝑛 − 𝑆𝑜𝑢𝑡 + 𝑆𝑔𝑒𝑛
○ 𝑆𝑔𝑒𝑛 ≥ 0 due to irreversibilities
○ If reversible process ⇒ 𝑆𝑔𝑒𝑛 = 0
● Entropy generation due to work
○ Energy is NOT transferred with work
○ BUT conversion of energy (from one type to another) does create entropy
𝑄
○ 𝑆ℎ𝑒𝑎𝑡 = 𝑇
(direction of Q depends on direction of heat transfer
■ Work out is often due to ∆𝑄 (perform energy balance)
■ Use temperature of immediate surroundings
 ● Entropy due to mass flow
○ Use mass specific entropy
○ 𝑆𝑚𝑎𝑠𝑠 = 𝑚 𝑠
● Performing energy balance
○ Use an extended system (include immediate surroundings)
𝑄𝑖𝑛 𝑄𝑜𝑢𝑡
○ 𝑆𝑖𝑛 = 𝑇𝑠𝑢𝑟𝑟
+ 𝑚𝑖𝑛 𝑠𝑖𝑛𝑙𝑒𝑡 𝑆𝑜𝑢𝑡 = 𝑇𝑠𝑢𝑟𝑟
+ 𝑚𝑜𝑢𝑡 𝑠𝑜𝑢𝑡𝑙𝑒𝑡
● Closed systems
○ Isolated system:
■ ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑆𝑔𝑒𝑛
○ Closed system:
𝑄𝑛𝑒𝑡, 𝑖𝑛
■ ∆𝑆 = 𝑇𝑠𝑢𝑟𝑟
+ 𝑚𝑖𝑛 𝑠𝑖𝑛 − 𝑚𝑜𝑢𝑡 𝑠𝑜𝑢𝑡 + 𝑆𝑔𝑒𝑛
● Open systems, control volume (CV)
○ Open system, steady-flow process, single-stream, adiabatic
■
○ Open system, steady-flow process, single-stream

Chapter 9 - Exergy
● Denoted: χ
○ Units: [J/kg] (mass basis)
● Available energy (useful work potential of system at given state)
● Maximum possible work
○ From given state to dead state (reversible process)
● Dead state (χ = 0)
○ At equilibrium with environment
𝑜
○ Assume: 𝑇 = 25 𝐶 and 𝑃 = 101 𝑘𝑃𝑎
● χ is Function of system & environment
What has exergy:
● All kinetic and potential energies is fully available
2
𝑉
● χ𝑘𝑒 = 2
● χ𝑝𝑒 = 𝑔𝑧
● χ𝑑𝑒𝑠𝑡𝑟𝑜𝑦𝑒𝑑 = 𝑇𝑜 𝑆𝑔𝑒𝑛 ≥ 0

Irreversibilities:
● Work on surroundings is lost
○ 𝑤𝑠𝑢𝑟𝑟 = 𝑊𝑏 = 𝑃𝑜 (𝑉2 − 𝑉1) where Po is pressure of surroundings
● ∴χ = 𝑤𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 = 𝑤𝑎𝑐𝑡𝑢𝑎𝑙 − 𝑤𝑠𝑢𝑟𝑟
 ● Denoted I
○ Wasted work potential
|
○ 𝐼 = 𝑋𝑟𝑒𝑣 − 𝑤𝑢𝑠𝑒𝑓𝑢𝑙 |
Second-law efficiency:
𝑤𝑢, 𝑜𝑢𝑡
● ηⅡ = 𝑤𝑟𝑒𝑣, 𝑜𝑢𝑡
(work producing)
𝑤𝑟𝑒𝑣, 𝑜𝑢𝑡
● ηⅡ = 𝑤𝑢, 𝑜𝑢𝑡
(work consuming)
𝐶𝑂𝑃
● ηⅡ = 𝐶𝑂𝑃𝑟𝑒𝑣
(refrigerator & heat pumps)

● ηⅡ ≤ 100%

Exergy change of system:

● Closed system (non flow)
○ Useful work/exergy
■ 𝑥𝑛𝑜𝑛𝑓𝑙𝑜𝑤 = (𝑢 − 𝑢𝑜) + 𝑃𝑜(𝑣 − 𝑣𝑜) − 𝑇𝑜(𝑠 − 𝑠𝑜) + 𝑘𝑒 + 𝑝𝑒
○ Exergy change
■ ∆𝑋 = 𝑋2 − 𝑋1 = 𝑚(𝑥𝑛𝑜𝑛𝑓𝑙𝑜𝑤,2 − 𝑥𝑛𝑜𝑛𝑓𝑙𝑜𝑤,1)
■ ∴ ∆𝑋 = 𝑚[(𝑢2 − 𝑢1) + 𝑃𝑜(𝑣2 − 𝑣1) − 𝑇𝑜(𝑠2 − 𝑠1) + ∆𝑘𝑒 + ∆𝑝𝑒]
● Open system (flow)
○ Flow energy/work:
■ 𝑤𝑓𝑙𝑜𝑤 = 𝑃𝑣
■ 𝑥𝑓𝑙𝑜𝑤 𝑜𝑛𝑙𝑦 = (𝑃 − 𝑃0)𝑣
■ ∆𝑥𝑡𝑜𝑡𝑎𝑙 = (ℎ2 − ℎ1) − 𝑇𝑜(𝑠2 − 𝑠1) + ∆𝑘𝑒 + ∆𝑝𝑒

Exergy transfer:
● Happens by
○ Heat
○ Work
○ Mass flow
● Via heat
𝑇𝑜
○ 𝑋ℎ𝑒𝑎𝑡 = (1 − 𝑇
)𝑄
■ For irreversible process ∴heat is heat converted in carnot heat engine
○ All heat is transferred
■ 𝑄1 = 𝑄2
○ Entropy is generated
𝑄 𝑄
■ 𝑇1
< 𝑇2

○ Exergy is destroyed
𝑇𝑜 𝑇𝑜
■ (1 − 𝑇1
)𝑄 > (1 − 𝑇2
)𝑄
● Work
 ○ Boundary work
■ 𝑋𝑤𝑜𝑟𝑘 = 𝑊 − 𝑊𝑠𝑢𝑟𝑟 (𝑊𝑠𝑢𝑟𝑟 = 𝑃𝑜(𝑉2 − 𝑉1), Po is atmospheric pressure)
○ Other work
■ 𝑋𝑤𝑜𝑟𝑘 = 𝑊
● Mass
○ 𝑋𝑚𝑎𝑠𝑠 = 𝑚[(ℎ − ℎ𝑜) − 𝑇𝑜(𝑠 − 𝑠𝑜) + 𝑘𝑒 + 𝑝𝑒]

Decrease of exergy principle:

● Exergy destroyed is linked to entropy created
○ Energy is only lost as non-useful, never created
● 𝑋𝑑𝑒𝑠𝑡𝑟𝑜𝑦𝑒𝑑 = 𝑇𝑜 𝑆𝑔𝑒𝑛

Exergy balance:
● Do entropy balance instead
● ∆𝑋𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑋𝑖𝑛 − 𝑋𝑜𝑢𝑡 − 𝑋𝑑𝑒𝑠𝑡𝑟𝑜𝑦𝑒𝑑
● Perform exergy balance on extended system
● To determine Wrev, set Xdestroyed=0
● Closed system
○ ∆𝑋𝑠𝑦𝑠𝑡𝑒𝑚 = 𝑋ℎ𝑒𝑎𝑡, 𝑖𝑛 + 𝑋𝑤𝑜𝑟𝑘, 𝑖𝑛 − 𝑋𝑑𝑒𝑠𝑡𝑟𝑜𝑦𝑒𝑑
● Open system
○ ∆𝑋𝐶𝑉 = 𝑋ℎ𝑒𝑎𝑡, 𝑖𝑛 + 𝑋𝑤𝑜𝑟𝑘, 𝑖𝑛 + 𝑋𝑚𝑎𝑠𝑠, 𝑖𝑛 − 𝑋𝑚𝑎𝑠𝑠, 𝑜𝑢𝑡 − 𝑋𝑑𝑒𝑠𝑡𝑟𝑜𝑦𝑒𝑑
● Steady flow
○ Perform rate basis