LECT.

4 THERMODYNAMICS
OVERVIEW
Dr. Ali Mahmoud Ali Attia
https://www.researchgate.net/profile/Ali_Attia2 1
Contents
◦ Analyses of gases mixtures as atmospheric air

◦ Volumetric and mass analysis

◦ Ideal gas mixture properties

◦ Combustion

◦ Laws of Thermodynamics for Reacting Systems

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Introduction to Gas Mixture
➢ Non-reacting gas mixture is mixture of two or more gases of fixed chemical composition. The
most common gases mixture is the atmospheric air; simply a mixture of nitrogen and oxygen needed
to compute amount of air needed to burn 1 kg/km of fuel.
➢ It is important to determine thermodynamic properties of a mixture to be able to understand
chemical reactions and fuel combustion.
➢ To evaluate mixture property, it’s necessary to know its composition, as well as, the properties of the
individual components i. So overall properties of mixture containing k elements will be expressed as:
➢ Total mass of the mixture: 𝑚𝑚 = 𝑚𝐴 + 𝑚𝐵 + 𝑚𝐶 +. . . = σ𝑘𝑖=1 𝑚𝑖
➢ The mole number of a mixture: 𝑁𝑚 = 𝑁𝐴 + 𝑁𝐵 + 𝑁𝐶 +. . . = σ𝑘𝑖=1 𝑁𝑖
➢ Then mixture composition can be described by specifying either the mass fraction mfi or the mole
𝑇ℎ𝑒 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖 𝑚𝑖
fraction yi of each component i: 𝑚𝑓𝑖 = =
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ 𝑒𝑚𝑖𝑥𝑡𝑢𝑟𝑒 𝑚𝑚
𝑚𝑖 1 𝑚𝑚
➢ Here summation of mass fractions: σ𝑘𝑖=1 𝑚𝑓 = σ𝑘𝑖=1 = σ𝑘𝑖=1 𝑚𝑖 = =1
𝑖 𝑚𝑚 𝑚𝑚 𝑚𝑚
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Introduction to Gas Mixture σ𝑘
𝑚𝑚 𝑖=1 𝑀𝑖 𝑁𝑖
➢ Mixture average molecular weight can be obtained as: 𝑀𝑚 = = = σ𝑘𝑖=1 𝑦𝑖 𝑀𝑖
𝑁𝑚 𝑁𝑚
𝑅𝑈
➢ Mixture gas constant is: 𝑅𝑚 = . where universal gas constant RU=8.314 kJ/kmol.K
𝑀𝑚
➢ Mass/gravimetric analysis is a mixture analysis based on mass fraction of each constituent.
➢ Volumetric analysis is a mixture analysis based on mole numbers or volume of each constituent in
the mixture.
➢ To change from a mass fraction analysis to a mole fraction analysis, we can show that:
𝑚𝑓 /𝑀𝑖 𝑚𝑓 /𝑀𝑖
𝑖
𝑦𝑖 = = 𝑘 𝑖
𝑀𝑚 σ𝑖=1 𝑀𝑓𝑖 Τ𝑀𝑖
➢ Example: Molar analysis of 100 kmole of air indicates that contains 79 kmole Nitrogen and 21
kmole Oxygen. Determine: (i) The mole fractions, (ii) The gravimetric analysis, (iii) Its molecular
weight, (iv) Its gas constant.
For simplicity use similar table:
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Introduction to Gas Mixture
𝑅𝑢
𝑅= = 0.288
𝑀𝑚

Element, No. of Moles fraction Molecular weight Mass of i Mass fraction

i yi [ni/nm] Mi [kg/kmole] mi=yiMi Mfi=mi/mm
O2 21 0.21 32 6.72 0.233
N2 79 0.79 28 22.12 0.767
mixture 100 1 1
𝑀𝑚 = ෍ 𝑦𝑖 . 𝑀𝑖 = 28.84

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Ideal Gases Analysis ሜ
➢ For mixture of ideal gases, the ideal gas law can e applied: 𝑃𝑉𝑚 = 𝑁𝑚 𝑅𝑇
➢ There are two major models for ideal gas mixture analysis; one for fixed pressure and temperature
(Amagat’s model), and the other for fixed volume and temperature (Dalton’s model)
➢ Amagat’s model: if each component in the mixture exists individually at the same pressure and
temperature of the mixture it will fill specific volume such that mixture total volume is the sum of
individual volumes of each component, or 𝑉𝑚 = σ𝑘𝑖=1 𝑉𝑖 𝑇𝑚 , 𝑃𝑚
➢ Dalton’s model: here each component occupies the same volume at the same temperature of the
mixture, so that mixture total pressure is the sum of each component partial pressures: 𝑃𝑚 =
𝑃 𝑁
σ𝑘𝑖=1 𝑃𝑖 𝑇𝑚 , 𝑉𝑚 , thus 𝑖 = 𝑖 = 𝑦𝑖
𝑃𝑚 𝑁𝑚

➢ Example: The products of coal combustion can be simplified as CO2 and N2 with concentration of
25 and 70% respectively. Find the mass analysis, the average molecular weight, average gas constant,
and mixture mass at 0.2 MPa and 27 ºC within a tank of volume 1 m3.
➢ The solution can be done in table like the following
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Ideal Gases Analysis
Element Mole fraction Molecular weight Mass of i Mass fraction
i yi [ni/nm] Mi [kg/kmole] mi=yiMi Mfi=mi/mm
CO2 0.3 44 13.2 0.4
N2 0.7 28 19.6 0.6
mixture 1 Mm=32.8 1
◦ Mixture gas constant: R=Ru/Mm=8.314/32.8=0.253 kJ/(kg.K)
◦ From ideal gas law, then mixture mas is: m=PV/(RT)=200*1/(300*0.253)=2.63 kg.
➢ In this case the mixture overall gas constant can be estimated from both the molar and the mass
fraction data as follows:
𝑅𝑢 𝑌𝑖
➢ 𝑅𝑚 = = 𝑅𝑢 σ𝑖=𝑛
𝑖=1 = σ𝑖=𝑛
𝑖=1 𝑅𝑖 𝑌𝑖 or
𝑀𝑚 𝑀𝑖
𝑅𝑢 𝑅𝑢 1
➢ 𝑅𝑚 = = = 𝑋𝑖
𝑀𝑚 σ𝑖=𝑛
𝑖=1 𝑋𝑖 𝑀𝑖 σ𝑖=𝑛
𝑖=1 𝑅𝑖

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Ideal Gas Mixture Properties
➢ Thermal properties: there are molar properties per unit of mole (indicated by dash above the
ሜ m ) and the commonly mass properties; per unit of mass. In reacting systems, it
property symbol; Cv
is common to use molar properties as chemical reactions are written in molar form.
➢ Specific gas constant at constant volume
ሜ m = Xa Cv
◦ Cv ሜ a + 𝑋b Cv
ሜ b + Xc Cv ሜ d = σ𝑖=𝑛
ሜ c + Xd Cv ሜ
𝑖=1 𝑋𝑖 Cv𝑖 kJ/kmol.K
➢ Specific gas constant at constant pressure:
ሜ m = X a Cp
◦ Cp ሜ a + 𝑋b Cp
ሜ b + X c Cp ሜ d = σ𝑖=𝑛
ሜ c + X d Cp ሜ
𝑖=1 𝑋𝑖 Cp𝑖 kJ/kmol.K
➢ And so any property like internal energy, enthalpy, entropy, and specific heat ratio;
◦ hሜ m = X a hሜ a + 𝑋b hሜ b + X c hሜ c + X d hሜ d = σ𝑖=𝑛 ሜ
𝑖=1 𝑋𝑖 h𝑖 kJ/kmol
◦ Sሜ m = X a Sሜ a + 𝑋b Sሜ b + X c Sሜ c + X d Sሜ d = σ𝑖=𝑛 ሜ
𝑖=1 𝑋𝑖 S𝑖 kJ/kmol.K

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Combustion
➢ Combustion process is rapid oxidation of reactant elements of fuel that release energy as well as
combustion products.
➢ During a combustion process the mass of each element remains constant. So the chemical equation
is balanced according to the mass conservation.
➢ The major combustible elements in fuels are carbon, hydrogen, and sulfur:
Reactants Products
𝐶 + 𝑂2 → 𝐶𝑂2
𝐻2 + 𝑂2 → 𝐻2 𝑂
𝑆 + 𝑂2 → 𝑆𝑂2
➢ As thermodynamics deals with equilibrium process, then it concerns with initial reactant and final
product not matter the intermediate reactions. Usual oxidation occurs using air. Air is composed of
21% oxygen and 79% nitrogen (by volume) or 23.3% oxygen and 76.7% nitrogen (by mass).
➢ Nitrogen is assumed to be not oxidized but it affects the temperature of the combustion products.
➢ For each 1 mole of oxygen, 79/21=3.76 moles nitrogen are involved, so there is 4.76 mole of air.
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Combustion
➢ Theoretical air: is the minimum amount of air that supplies sufficient oxygen for complete
combustion of all carbon, hydrogen, and any oxidized element in the fuel.
➢ For 1 mole of hydrocarbon CxHy the general reaction is:
CnHm+aO2(O2+3.76N2)→aCO2CO2+aH2OH2O+aN2N2
➢ The stoichiometric (theoretical) coefficients are obtained from the balance of atoms :
◦ C: aCO2=n
◦ H: 2 aH2O=m
◦ N2: aN2=3.76*aO2
◦ O2: aO2=aCO2+ aH2O/2 =n+m/4
➢ Thus number of air moles for 1 mole of fuel becomes: Nair=aO2*4.76=4.76(n+m/4)
𝑚
m 𝑛+ ∗4.76∗28.85
= air = 𝑎𝑖𝑟 𝑎𝑖𝑟 =
𝑛 𝑀
➢ Air-to-fuel ratio is expressed based on mass basis: 𝐴𝐹𝑚𝑎𝑠𝑠 4
m
fuel 𝑛𝑓𝑢𝑒𝑙 𝑀𝑓𝑢𝑒𝑙 𝑛∗12+𝑚

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Combustion
➢ The equivalence ratio () is the actual fuel-air ratio divided by the theoretical fuel-air ratio (the
reciprocal of theoretical percent): Φ = 𝐹𝐴/𝐹𝐴 𝑇ℎ ≡ 𝐴𝐹𝑇ℎ /𝐴𝐹
➢ In actual combustion process AF may be greater than AFTh (excess air or <1 lean mixture) or
𝐴𝐹−𝐴𝐹𝑇ℎ
smaller than AFTh (insufficient air or >1 rich mixture). Excess air factor: 𝑋 =
𝐴𝐹𝑇ℎ

➢ The enthalpy of formation/combustion of a compound is the quantity of energy absorbed (or

released) during its formation from its elements (end pressures and temperatures being maintained
equal at reference conditions 298K, 0.1MPa).
➢ 𝑄𝐶.𝑉. + 𝐻𝑅 = 𝐻𝑃 where Subscripts R and P refer to reactants and products
➢ Thus 𝑄𝐶.𝑉. + σ𝑅 𝑛𝑖 ℎሜ 𝑖 = σ𝑃 𝑛𝑒 ℎሜ 𝑒 . For reaction of C with O2 HR =0, then: 𝑄𝐶.𝑉. = 𝐻𝑃 =
− 393522 kJ/kmol. thus for CO2 , ℎሜ 𝑓𝑜 = −393522 kJ/kmol
➢ Note that, Enthalpy of element in any state rather than reference one is:
➢ ℎሜ 𝑇,𝑃 = ℎሜ 𝑜 298,0.1𝑀𝑃𝑎 + Δℎሜ 𝑜 298,0.1𝑀𝑃𝑎→𝑇,𝑃 or simply ℎሜ 𝑇,𝑃 = ℎሜ 𝑜𝑓 + Δℎሜ
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◦ Stable elements as O2
and N2, at 25°C have
zero enthalpy of
formation.
◦ Heating value: is
negative the enthalpy
of combustion.
◦ Higher heating value is
attained when produced
water is condensed.
◦ Lower heating value is
attained when water
product still in vapor
phase; which is the
common practical case.
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Note that: theoretical mixture is called 100%
theoretical air. While other actual mixture can be
expressed in manner of reciprocal of equivalence
ratio called percent theoretical air expressed as a
fraction of the theoretical amount. Thus, 150%
theoretical air means that the air actually supplied is
1.5 times the theoretical air and the equivalence
ratio is 2/3.
Actual reaction for x excess ir factor is:
𝐶𝑛 𝐻𝑚 + 𝑎𝑡ℎ 1 + 𝑥 𝑂2 + 3.76𝑁2
𝑚
→ 𝑛𝐶𝑂2 + 𝐻2 𝑂 + 𝑥𝑎𝑡ℎ 𝑂2 + 3.76. 𝑎𝑡ℎ (1
2
+ 𝑥)𝑁2
Here the A/F ratio is:
𝑚
(1+𝑥) 𝑛+ ∗4.76∗28.85
4
𝐴𝐹𝑚𝑎𝑠𝑠 =
𝑛∗12+𝑚
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Laws of Thermodynamics for Reacting Systems
➢ 1st Law of thermodynamics (Energy Analysis): 1st law for steady state-steady flow combustion
process has the following form: 𝑄𝑐.𝑣. + 𝐻𝑅 = 𝐻𝑃 + 𝑊𝑐.𝑣. or:
𝑄𝑐.𝑣. + ෍ 𝑛𝑖 (ℎሜ 𝑓,𝑖
𝑜
+ Δℎሜ 𝑖 ) = ෍ 𝑛𝑒 (ℎሜ 𝑓,𝑒
𝑜
+ Δℎሜ 𝑒 ) + 𝑊𝑐.𝑣.
𝑅 𝑃
➢ Where R and P refer to reactants and products, respectively. In each problem it is necessary to
choose one parameter as the basis of the scaling, so 1 kmol of fuel is usually used.

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Laws of Thermodynamics for Reacting Systems
➢ In actual reacting systems, reactants and products are not at a temperature of 25°C and a pressure of
0.1 MPa (the state at which the enthalpy of formation is given). Moreover, fuel may exist as solid or
liquid, so additional enthalpies are needed as given in thermodynamic property tables. For gases, it is
common to have thermodynamic data table where Δℎሜ 𝑖 can be found directly as a function of only
temperature. Then ideal gas law is applied to get pressure change for closed system only. In some
cases, like for fuel, other temperature are given so, its relation of specific heat should be known to
𝑇
get the change in enthalpy: ∆ℎത 𝑇 − 𝑇0 = ‫𝑃𝐶 𝑜𝑇׬‬ҧ 𝑇 𝑑𝑇.
➢ The general form of 1st Law in reacting system:
➢ ℎሜ 𝑅𝑃 = 𝐻𝑃 − 𝐻𝑅 = σ𝑃 𝑛𝑒 (ℎሜ 𝑓,𝑒
𝑜
+ Δℎሜ 𝑒 ) − σ𝑅 𝑛𝑖 (ℎሜ 𝑓,𝑖
𝑜
+ Δℎሜ 𝑖 )with fixed enthalpy of formation:
➢ 𝐻𝑅𝑜 = σ𝑅 𝑛𝑖 ℎሜ 𝑓,𝑖
𝑜
and Δ𝐻𝑅 = σ𝑅 𝑛𝑖 Δℎሜ 𝑖
➢ 𝐻𝑃𝑜 = σ𝑃 𝑛𝑒 ℎሜ 𝑓,𝑒
𝑜
and Δ𝐻𝑃 = σ𝑃 𝑛𝑒 Δℎሜ 𝑒
➢ 𝐻𝑃 − 𝐻𝑅 = 𝐻𝑃𝑜 − 𝐻𝑅𝑜 + Δ𝐻𝑃 − Δ𝐻𝑅 𝑜
⇒ 𝐻𝑃 − 𝐻𝑅 = Δ𝐻𝑅𝑃 + Δ𝐻𝑃 − Δ𝐻𝑅
15
◦ Adiabatic flame temperature is the temperature of combustion products due to adiabatic
combustion process which is the maximum achieved temperature for a given reactants. The maximum
adiabatic flame temperature is achieved at the stoichiometric mixture.
◦ 𝐻𝑃 = 𝐻𝑅 or σ𝑃 𝑛𝑒 (ℎሜ 𝑓,𝑒
𝑜
+ Δℎሜ 𝑒 ) = σ𝑅 𝑛𝑖 (ℎሜ 𝑓,𝑖
𝑜
+ Δℎሜ 𝑖 )as enthalpy depends on T, then try−and−error
is used to calculate T by assuming its value and check that it is satisfy the adiabatic condition. 16
◦ In case of closed volume systems as in the internal combustion engines, the combustion process is
called constant volume combustion. here internal energy is constant rather than enthalpy and the
ideal gas law is needed to determine the final pressure.
◦ 𝑢lj 𝑅𝑃 = 𝑈𝑃 − 𝑈𝑅 thus: 𝑢lj 𝑅𝑃 = ℎሜ 𝑅𝑃 − 𝑅𝑢 𝑛Pr 𝑜𝑑𝑢𝑐𝑡 𝑇𝑒 − 𝑛Re 𝑎𝑐 tan 𝑡 𝑇𝑖
𝑃𝑒 𝑃𝑅
◦ Note that the above equation is solve by tray and error to get final temperature. Then =
𝑛𝑃 𝑇𝑒 𝑛𝑅 𝑇𝑅
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Laws of Thermodynamics for Reacting Systems
➢ 2nd Law of thermodynamics (Energy Analysis): There exists a thermodynamic state function,
called entropy, S, whose difference with surrounding shall be greater than zero ΔSUnivrsezero
➢ note that combustion process has great level of irreversibility not only due to heat transfer but also
due to mass transfer, so there is a corresponding loss of availability (exergy); thus Wrev= Greactant-
Gproduct. Where The G is the Gibbs function or ‘Gibbs free energy’ G is defined as: G=H-TS.
➢ Irreversibility is main core for chemical reaction equilibrium; this topic will be presented latter.
➢ For steady state chemical reaction process the reversible work is:
➢ ⇒ 𝑊𝑟𝑒𝑣 = σ𝑅 𝑛𝑖 ℎሜ 𝑓𝑜 + Δℎሜ − 𝑇𝑜 𝑠lj − σ𝑃 𝑛𝑒 ℎሜ 𝑓𝑜 + Δℎሜ − 𝑇𝑜 𝑠lj = −Δ𝐺
𝑖 𝑒
➢ Irreversibility for such process is the difference between reversible and actual work:
➢ 𝐼 = 𝑊𝑟𝑒𝑣 − 𝑊 = σ𝑃 𝑛𝑒 𝑇𝑜 𝑠lj𝑒 − σ𝑅 𝑛𝑖 𝑇𝑜 𝑠lj𝑖 − 𝑄𝑐.𝑣.
➢ 3rd Law of thermodynamics states that the entropy of a perfect crystal is zero at absolute zero, so it defines
the absolute value of entropy.
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THANK YOUR

Waiting your questions

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