AA284a

Advanced Rocket Propulsion

Lecture 3
Review of Thermodynamics and Chemistry

Prepared by
Arif Karabeyoglu

Mechanical Engineering
KOC University

Fall 2019

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Advanced Rocket Propulsion
Review of Thermodynamics-Definitions
• System: A group of entities distinguished from its
surroundings
– Mass and energy transfer is allowed
– Change of volume is allowed
– Example: Human body
• Transfer quantities
– Heat (transfer to the system): δ Q
– Work (done by the system): δ W
– Mass transfer: δ M
• Definitions:
– Open System: Mass transfer allowed
– Closed System: Mass transfer not allowed
– Adiabatic System: Heat transfer is not allowed
Reference on Thermodynamics: I. Klotz and R. Rosenberg, “Chemical Thermodynamics”
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Review of Thermodynamics-Definitions
• State of the system: Quantify the status of the system
– Extrinsic properties: E, H, G, M, N
– Intrinsic properties: T, P, z, K
– Extrinsic properties can be converted to intrinsic properties
• Example: e=E/M
• Change of State:
– Potential drives the system to change
– When the potential diminishes system reaches an equilibrium.
• Mission of Thermodynamics
– Governs the rules of change of state
– Move from state A to state B is feasible or not for specified heat
and mass transfer and work done
– Thermodynamics does not answer the questions how fast or what
is the exact form of the process.
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Review of Thermodynamics-Laws
• Zeroth Law:
– If A is in equilibrium with C and B is in equilibrium with C, than A
and B must be in equilibrium.
• First Law:
– Conservation of energy
– Change in the internal energy must be equal to the heat added to
the system minus the work done by the system

d e = δ q −δ w
e : Internal Energy
– For simple materials only work is the pressure work. h : Enthalpy

δ w = P dv q : Heat Transfer
w : Work Done
– In terms of enthalpy P : Pr essure
d h = δ q + v dP v : Specific Volume
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Review of Thermodynamics-Laws
• Second Law:
– Reversible/Irreversible processes
• Imagine a time dependent physical process governed by a set of
equations
• If these equations are invariant with regard to the sign of the time
variable the process is reversible, else irreversible
– There exists a system variable, entropy, with the following
definition for a single component system
δq δQ
d s= dS=
T T
• Explicit property
S : Entropy
– Second law of thermodynamics
s : Specific Entropy
d Suniverse ≥ 0 T : Temperature

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Review of Thermodynamics-Laws
• Second Law:
– Or

d S system + d S surroundings ≥ 0
– For an isolated system
d Ssystem ≥ 0
– Entropy is a measure of “disorder” or lack of “information” on the
possible microstates
– Boltzmann’s Equation: S = k ln(N micro )
– All real processes are irreversible k : Boltzmann' s Cons.
• Third Law: N mic : Number of Micro States
– Planck’s Formulation: Value of entropy of a pure liquid or solid
approaches zero at 0 K
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Review of Thermodynamics-Cycles
• Heat machines convert thermal energy into mechanical energy according to the
laws of thermodynamics.
• Many machines work in cycles. Working fluid returns to the original state that it
started.
• Carnot Cycle:
– Two constant temperature heat transfer processes and two isentropic
compression expansion processes
Q T η : Efficiency
– Carnot cycle efficiency: ηC = 1 − 1 = 1 − 1
• Bryton Cycle: Q2 T3
– Two constant pressure heat transfer processes and two isentropic
compression expansion processes
Δhcooling T T
– Bryton cycle efficiency: ηB = 1 − =1− 1 <1− 1
Δhheating T2 T3
• Cycle efficiency increases with increasing temperature ratio
• Carnot cycle is always the best efficiency heat machine operating
between two specified temperature extremes (T1 and T3).

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Review of Thermodynamics-Carnot Cycle

Q2 Δhcooling T1
s3 − s2 = ηB = 1 − = 1−
T2 Δhheating T2

W Q2 − Q1 Q
• Carnot Cycle Efficiency ηC = = = 1− 1
Q2 Q2 Q2
Q Q
• Isothermal/Isentropic Branches: s1 − s4 = − 1 s3 − s2 = 2 s2 = s1 s3 = s4
T1 T2
• Combine:
Q2 Q1
=
T2 T1 ⇒ T T T
ηC = 1 − 1 = 1 − 1 = 1 − cold
T2 T3 Thot
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Review of Thermodynamics - Bryton Cycle

Q1 h −h
• Bryton Cycle Efficiency ηB = 1− = 1− 4 1
Q2 h3 − h2
T4 − T1
• Perfect Gas: ηB = 1−
T3 − T2
T4 T1
• From Isentropic and Isobaric Branches: =
T3 T2

Stanford University
⇒ ηB = 1 −
T1
T2
but T3 = Thot > T2

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Review of Thermodynamics – Cycle Comparison
• Work done by the fluid

W = ∫ P dv
• For the same extreme
temperatures the Carnot cycle is
more efficient than the Bryton cycle
• This conclusion is valid for all other
cycles.
• Thus Carnot cycle sets the upper
limit for the efficiency of a heat
engine operating at two set
temperatures
• Nonideal behavior is due to
– Non-isothermal heat transfer
– Non-isentropic expansion and
compression
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State Equation
• State equation relates the state variables of a substance to
each other
• Gibb’s Phase Rule:
Number of Phases + Independent Intensive Properties
=
2 + Number of Components

( P + V = C +2 )
– Examples
• If P=1 and C=1, V=2 (One phase one component)
• If P=2 and C=1, V=1 (Two phase one component)
• If P=1 and C=2, V=3 (One phase two component)
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State Equation
• State Equation for a one component system:

f (P, v, T ) = 0 P = P(v, T )

• Examples
– Ideal Gas Equation:
P=ρ RT

– Ideal Liquid Equation:

ρ = cons.

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Real Gases
• Ideal gas approximation fails at high pressures/low temperatures
– Volume of the gas molecules become non trivial
– Attraction/repulsion forces between molecules become significant
• Real gas. Compressibility factor (read z from charts)
P P Vm
z≡ = Vm : Molar Volume
ρ R T Ru T
• Equation of State (EOS) for real gases (Cubic equations)
– Van der Waals
⎛ a ⎞
⎜ P + 2 ⎟ (Vm − b ) = RuT
⎜ Vm ⎟⎠
⎝
– Redlich-Kwong EOS

⎛ a ⎞ 0.0866 R Tc PcVm 1
⎜ P + 0.5 ⎟ (Vm − b ) = RuT 0.42748 R 2Tc2.5 b= zc= =
⎜
⎝ (
T Vm Vm − b ) ⎟
⎠
a=
Pc Pc RuTc 3

– Peng-Robinson EOS RuT a(T )

P= −
Vm − b Vm (Vm + b) + b (Vm − b)
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P-V-T Diagram of a Single Component Substance

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P-h Diagram Molecular Oxygen

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Saturation Pressure and Density Plots for N2O

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Saturation Pressure vs Saturation Density for Popular Oxidizers

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Specific Heats
• Specific heats are defined as
c p : Specific Heat @ Cons. Pr essure
∂h ∂e cv : Specific Heat @ Cons. Volume
cp = cv =
∂T P ∂T v
γ : Ratio of Specific Heats
• For an ideal gas h = h(T ) e = e(T )
dh de cp
cp = cv = c p − cv = R γ=
dT dT cv

• For a calorically perfect gas both specific heats are constant

N +2 N
cp = R cv = R
2
• N is the internal 2
degrees of freedom (fully excited)

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Specific Heats
• Monotonic gas: N=3 (3 translational DoF)
• Diatomic gas
– Vibrational modes NOT excited: N=5 (+2 rotational DoF)
– Vibrational modes fully excited: N=7 (+2 vibrational DoF)
2
⎛ Θv ⎞ e Θv T
(cv )vib =R⎜ ⎟
– For intermediate temperatures
hν
(
⎝ T ⎠ e Θv T − 1 )
2

Θv ≡ = Characteristic Temperature for Vibration ν = Frequency

k
– Data for diatomic molecules h : Planck' s Cons.

Characteristic Temperature N2, K O2, K

Rotational 2.9 2.1
Vibrational 3,390 2,270
Dissociation 113,000 59,500
Ionization 181,000 142,000
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Thermal Rocket – General Concept
• In a thermal rocket the propellant molecules are thermalized by addition of heat
in a chamber.
• This thermal energy (random motion of the molecules) is converted to the useful
directional velocity needed for thrust in the nozzle.

• The heat source varies

– Nuclear energy: Thermonuclear rockets
– Chemical bond energy: Chemical rockets
– Electric energy: Resistojets and Arcjets
– Thermal energy of the stored propellant: Cold gas thrusters
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Thermal Rocket – Thermodynamic Process
• Note that this is not really a cycle
since the propellant never returns to
its original state
• The velocity at the nozzle exit, ue,
can be estimated using the
conservation of energy along a
streamline
1
htc − he = ue2
2
ue = 2 (htc − he )
c p − cv = RT
• The maximum possible exit velocity
(or Isp) is obtained for infinite
expansion (he=0)
• For monatomic gas: ue = 2 htc
• For calorically perfect gas
RuTtc
ue = 2.21 2γ RuTtc
Mw ue =
γ −1 Mw
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Thermal Rocket – Velocities in Monatomic Gas
• Lets compare this maximum velocity to the other fundamental velocities that
can be defined in a monatomic gas
RuTtc Isentropic Speed of Sound : a = 1.29 RuTtc
Maximum Directional Velocity : ue = 2.21 s
Mw Mw

RT RuTtc
CharactristicVelocity : c* = 1.38 u tc Isothermal Speed of Sound : aT =
Mw Mw
RuTtc
Most Probable Molecular Speed (Maxwellian Distribution) : CMP = 1.41
Mw
RuTtc
Average Molecular Speed (Maxwellian Distribution) : C = 1.60
Mw
12 RuTtc
Square Averge Molecular Speed : ⎛⎜ C 2 ⎞⎟ = 1.72
⎝ ⎠ Mw
• Note that all of these speeds are of the same order (order of the average speed
of the molecules in the gas)
• Similar results can be produced for other gamma values

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Review of Chemistry
• Atomic Model: Negatively charged electrons are orbiting around the positively
charged nucleus
• Schrodinger’s wave equation governs the size, number and shape of the orbitals

⎡ h2 2 Z e2 ⎤
⎢− 2 ∇ − ⎥Ψ = E Ψ
⎣ 8π me r ⎦
• Square norm of the wave function is a probability density function for the position
or momentum of the electron
• Eigenvalue problem – Only discrete levels of energy is possible

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Review of Chemistry – Energy Level Diagrams
Atomic Structure (Quantum Mechanics)
• Principal quantum number: n=1, 2, 3 …
– General energy level of the shell
– n=1 (K), n=2 (L), n=3 (M),…
• Angular momentum quantum number: l=0, 1,
…(n-1) [Orbital angular momentum]
– Determines the shape of the orbitals
– l=0 (s), l=1 (p), l=2, (d), …
• Magnetic quantum number: ml: +l, +l-1,…0,
…-(l-1), l
– Determines the number of orbitals
• Electron Spin quantum number, ms
– Each electron has: s=½ or -½ [Intrinsic
angular momentum the electron]

Pauli Exclusion Principle:

“No two electrons in an atom may posses
identical sets of values of the four
quantum numbers n, l, ml,, ms “

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Review of Chemistry
• Quantum Mechanics Predicts:
n : Pr incipal Quantum Number
– Shells, subshells, orbitals
• n=1: K shell (2 electrons)
– 1s subshell (1 orbital): electrons
• n=2: L shell (8 electrons)
– 2s subshell (1 orbital): 2 electrons
– 2p subshell (3 orbitals): 6 electrons
• n=3: M shell
– 3s subshell (1 orbital): 2 electrons
– 3p subshell (3 orbitals): 6 electrons
– 3d subshell: (5 orbitals): 10 electrons
• Argononic structures: Completely full shells (Noble elements: He,
Ne, Ar …), Octets
• Valance electrons: Electrons in the shell that is not completely
filled

Reference on Chemistry: Linus Pauling, “General Chemistry”

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Periodic Table of Elements

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Review of Chemistry
• Elements in the same group have closely related physical and chemical
properties (same number of valance electrons)
• Elements in the periods have their valance electrons in the same shell
• Left side of the periodic table : Metals (Fuels)
– High electric and thermal conductivity, metallic luster, malleable,
ductile
• Right side of the periodic table : Nonmetals (Oxidizers)
• Metalloids in the middle: B, Si, Ge, As
• Chemical Bonds:
– Octet rule: Filled shell rule
• Share or gain electrons to fill their shells to the Argononic structures
– Covalent Bonds: Share pairs of electrons (H-C)
– Ionic Bonds: Take or give electrons (Li+Cl-)
• Electronegativity: Affinity of an atom to an electron
– The difference in electronegativity determines the covalent/ionic nature of the
bond (Upper right highly electronegative, lower left poorly electronegative)
• Strained bonds (C3H6, C2H2) and Resonance Structures (N2O)

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Review of Chemistry – Electronegativity of the Elements
Electronegativity of the Elements (Pauling Scale)

(
3590 Z eff − 0.35 ) + 0.744
Allred-Rochow Scale Electronegativity Coefficients: χ = 2
rcov

Z eff : Effective Atomic Number rcov : Covelent Radius

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Review of Chemistry – Electronegativity and Bonding
Influence of Electronegativity on Chemical Bonding

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