ME 475/675 Introduction to

Combustion
Lecture 3

Thermodynamic properties of pure, mixtures and reacting systems

Announcement
• Dilesh will hold a problem session
• Tuesday 10 am or 4 pm. Which time?
• HW 1 due Wedensday
• Chapter 2 (2, 8, 12, 13, X1)
• Problem X1
• Consider the broad education necessary to understand the impact of engineering
solutions (Introduction to Combustion) in a global and societal context
• Read a news article that describes some issue related to combustion
• For example: Energy efficiency, pollution, range land fires, fire safety, nuclear safety
• In one paragraph, summarize the article, and indicate how it is related to your interest in
combustion and/or this class
Thermodynamic Systems (reactors)
1𝑊2 Inlet i Outlet o

𝑚ሶ 𝑖 𝑒 + 𝑃𝑣 𝑖 Dm=DE=0 𝑚ሶ 0 𝑒 + 𝑃𝑣 𝑜

1𝑄2 m, E

𝑄ሶ 𝐶𝑉 𝑊ሶ 𝐶𝑉
• Closed systems
𝑣22 𝑣12
• 1𝑄2 − 1𝑊2 = 𝑚 𝑢2 − 𝑢1 + − + 𝑔 𝑧2 − 𝑧1
2 2
• Open Steady State, Steady Flow (SSSF) Systems
𝑣𝑜2 𝑣𝑖2
• 𝑄ሶ 𝐶𝑉 − 𝑊ሶ 𝐶𝑉 = 𝑚ሶ ℎ𝑜 − ℎ𝑖 + − + 𝑔 𝑧𝑜 − 𝑧𝑖
2 2
• How to find changes, 𝑢2 − 𝑢1 and ℎ𝑜 − ℎ𝑖 , for mixtures when temperatures and
composition change due to reactions (not covered in Thermodynamics I)
Calorific Equations of State for a pure substance
• 𝑢 = 𝑢 𝑇, 𝑣 = 𝑢(𝑇) ≠ 𝑓𝑛(𝑣) • Specific Heats, 𝑐𝑣 and 𝑐𝑃 [kJ/kg K]
• Energy input Q to increase temperature of
• ℎ = ℎ 𝑇, 𝑃 = ℎ(𝑇) ≠ 𝑓𝑛(𝑃) one kg of a substance by 1°C at constant
For ideal gases volume or pressure
• Differentials (small changes) • How are 𝑐𝑣 𝑇 and 𝑐𝑃 𝑇 measured?
𝑐𝑝
𝜕𝑢 𝜕𝑢 𝑐𝑣 T [K] Q [joules]
• 𝑑𝑢 = 𝑑𝑇 + 𝑑𝑣 w
𝜕𝑇 𝑣 𝜕𝑣 𝑇
Q m, T
𝜕ℎ 𝜕ℎ Q
• 𝑑ℎ = 𝑑𝑇 + 𝑑𝑃 m, T
𝜕𝑇 𝑃 𝜕𝑃 𝑇 1 kg
• For ideal gas 1 kg
𝜕𝑢 𝜕𝑢
• = 0; = 𝑐𝑣 𝑇 V = constant P = wg/A = constant
𝜕𝑣 𝑇 𝜕𝑇 𝑣
• 𝒅𝒖 = 𝒄𝒗 𝑻 𝒅𝑻 𝑄 𝑘𝐽
𝜕ℎ 𝜕ℎ • Calculate 𝑐𝑝 𝑜𝑟 𝑐𝑝 =
• = 0; = 𝑐𝑃 𝑇 𝑚Δ𝑇 𝑝 𝑜𝑟 𝑣 𝑘𝑔𝐾
𝜕𝑃 𝑇 𝜕𝑇 𝑃
• 𝒅𝒉 = 𝒄𝑷 𝑻 𝒅𝑻 • Molar based
𝑘𝐽
• 𝑐𝑝ҧ = 𝑐𝑝 ∗ 𝑀𝑊; 𝑐𝑣ҧ = 𝑐𝑣 ∗ 𝑀𝑊
𝑘𝑚𝑜𝑙 𝐾
Molar Specific Heat Dependence on Temperature

𝑐𝑝ҧ 𝑇
𝑘𝐽
𝑘𝑚𝑜𝑙 𝐾

• Monatomic molecules:
• Only possess translational kinetic energy 𝑇 [K]
• All energy input increases kinetic energy (associated with temperature)
• 𝑐𝑝ҧ 𝑇 nearly independent of temperature
• Multi-Atomic molecules: Increase with temperature and number of molecules
• Also possess rotational and vibrational kinetic energy (only fraction of energy goes to
kinetic)
• 𝑐𝑝ҧ 𝑇 increases with temperature as energy gets diverted to more modes
Specific Internal Energy and Enthalpy
• Once 𝑐𝑣ҧ 𝑇 and 𝑐𝑝ҧ 𝑇 are known, specific enthalpy h(T) and internal energy u(T) can be
calculated by integration
𝑇
• 𝑢ത 𝑇 = 𝑢ത 𝑟𝑒𝑓 + ‫𝑇׬‬ 𝑐𝑣ҧ 𝑇 𝑑𝑇
𝑟𝑒𝑓
𝑇
ത ത
• ℎ 𝑇 = ℎ𝑟𝑒𝑓 + ‫𝑇׬‬ 𝑐𝑝ҧ 𝑇 𝑑𝑇
𝑟𝑒𝑓
𝑇2
ത ത
• Primarily interested in changes, i.e. ℎ 𝑇2 − ℎ 𝑇1 = ‫𝑝𝑐 𝑇׬‬ҧ 𝑇 𝑑𝑇,
1
• When composition does not change 𝑇𝑟𝑒𝑓 and ℎത 𝑟𝑒𝑓 are not important
• Tabulated and Curve Fit: Appendix A, pp. 687-699
• For combustion gases: CO, CO2, H2, H, OH, H2O, O, N, NO, NO2, O2
• bookmark (show tables) T, 𝑐𝑝ҧ , ℎ𝑓𝑜 𝑇 − ℎ𝑓𝑜 298 = ℎത 𝑇 − ℎത 298𝐾 ,…
• Superscript o (ℎ𝑓𝑜 ) is for 1 atm, not important for ideal gas
• Curve fits for Fuels, Appendix B, Page 702
• Use in spreadsheets
• 𝑐𝑣ҧ = 𝑐𝑝ҧ − 𝑅𝑢
• 𝑐𝑝 =𝑐𝑝ҧ /𝑀𝑊; 𝑐𝑣 =𝑐𝑣ҧ /𝑀𝑊
Mixture Properties
• Extensive Enthalpy • Use these relations to calculate
• 𝐻𝑚𝑖𝑥 = σ 𝑚𝑖 ℎ𝑖 = 𝑚 𝑇𝑜𝑡𝑎𝑙 ℎ𝑚𝑖𝑥 mixture specific enthalpy and internal
σ 𝑚 𝑖 ℎ𝑖 energy (per mass or mole) as functions
• 𝒉𝒎𝒊𝒙 (𝑻) = = σ 𝒀𝒊 𝒉𝒊 (𝑻) of the properties of the individual
𝑚𝑇𝑜𝑡𝑎𝑙

• 𝐻𝑚𝑖𝑥 = σ 𝑁𝑖 ℎത 𝑖 = 𝑁𝑇𝑜𝑡𝑎𝑙 ℎത 𝑚𝑖𝑥 components and their mass or molar

ഥ𝒎𝒊𝒙 (𝑻) = ഥ𝑖
σ 𝑁𝑖 ℎ
ഥ𝒊 (𝑻)
fractions.
•𝒉 = σ 𝝌𝒊 𝒉
𝑁𝑇𝑜𝑡𝑎𝑙
• For ideal gases, u and h depend on
temperature, but not pressure
• Specific Internal Energy
• 𝒖𝒎𝒊𝒙 (𝑻) = σ 𝒀𝒊 𝒖𝒊 (𝑻)
•𝒖ഥ 𝒎𝒊𝒙 𝑻 = σ 𝝌𝒊 𝒖 ഥ𝒊 𝑻
Standardized Enthalpy and Enthalpy of Formation
• Needed to find 𝑢2 − 𝑢1 and ℎ𝑜 − ℎ𝑖 for chemically-reacting masses because
energy is required to form and break chemical bonds
• Not considered in Thermodynamics I
• ℎത 𝑖 𝑇 = ℎത𝑓,𝑖
𝑜
𝑇𝑟𝑒𝑓 + Δℎത 𝑠,𝑖 (𝑇)
• Standard Enthalpy at Temperature T =
• Enthalpy of formation from “normally occurring elemental compounds,” at standard
reference state: 𝑇𝑟𝑒𝑓 = 298 K and P° = 1 atm
𝑇
• Sensible enthalpy change in going from Tref to T = ‫𝑇׬‬ 𝑐𝑝ҧ 𝑇 𝑑𝑇
𝑟𝑒𝑓

• Normally-Occurring Elemental Compounds

• Examples: O2, N2, C, He, H2
• Their enthalpy of formation at 𝑇𝑟𝑒𝑓 = 298 K are defined to be ℎത𝑓,𝑖
𝑜
𝑇𝑟𝑒𝑓 = 0
• Use these Normally-Occurring compounds as bases to tabulate the energy to form other
compounds
Standard Enthalpy of O atoms

298K

• Experiments show that to form 2O atoms from one O2 molecule requires 498,390
kJ/kmol of energy input to break O-O bond (initial and final T= 298K and P= 1atm)
• At 298K: (1 mole) O2 + 498,390 kJ  (2 mole) O
498,390 kJ 𝑘𝐽
• ℎത𝑓,𝑂
𝑜
𝑇𝑟𝑒𝑓 = = + 249,195
2 𝑘𝑚𝑜𝑙𝑂 𝑘𝑚𝑜𝑙𝑂
• energy input to form 1 mole O from 0.5 mole O2 (normally-occurring form of O)
• ℎത𝑓,𝑖
𝑜
𝑇𝑟𝑒𝑓 for other compounds are in Appendices A and B, pp 687-702
• To find enthalpy of O at other temperatures use
• ℎത 𝑂2 𝑇 = ℎത𝑓,
𝑜 ത
𝑂2 𝑇𝑟𝑒𝑓 + Δℎ𝑠, 𝑂2 (𝑇) (Appendix A)
Example:

• Problem 2.14, p 71: Consider a stoichiometric mixture of isooctane and

air. Calculate the enthalpy of the mixture at the standard-state
temperature (298.15 K) on a per-kmol-of-fuel basis (kJ/kmolfuel), on a
per-kmol-of-mixture basis (kJ/kmolmix), and on a per-mass-of-mixture
basis (kJ/kgmix).
• ID: Find enthalpy at 298.15 K on different bases

• Problem 2.15: Repeat for T = 500 K

• do this in lecture 4
 Standard Enthalpy of Isooctane

298.15 0.29815
a1 a2 a3 a4 a5 a6 a8
-0.55313 181.62 -97.787 20.402 -0.03095 -60.751 20.232
h [kJ/Kmol] -224108.82 -0.16492 8.072412 -0.8639 0.040304 0.103807 -60.751

• Coefficients 𝑎1 to 𝑎8 from Page 702

𝑇 [𝐾]
• 𝜃= ;
1000 𝐾
ത 𝑜 𝑘𝐽 𝜃2 𝜃3 𝜃4 𝑎5
• ℎ = 4184(𝑎1 𝜃 + 𝑎2 + 𝑎3 + 𝑎4 − + 𝑎6 )
𝑘𝑚𝑜𝑙𝑒 2 3 4 𝜃
• Spreadsheet really helps this calculation