Chemical Reactions

Objectives: •Apply the conservation of mass to reacting systems to determine balanced reaction equations. •Defined the parameters used in combustion analysis, such as air-fuel ratio, percent theoretical air, and dew point temperature. •Apply energy balance to reacting systems for both steadyflow control volumes and fixed mass systems. •Calculate enthalpy of reaction, enthalpy of combustion, and the heating value of fuels. •Determine the adiabatic flame temperature for reacting mixture.

Combustion of fuel Æ Heat Æ Heat Engine Æ Work Combustion of fuel Æ Chemical Reaction How much fuel is needed? How about the air used? How high the combustion flame temperature will be?

Steam Generator

Rocket Engine

Jet Engine Piston Engine

1

Fuels
• Fossil Fuels: Coal, Petroleum, Natural Gases (LNG: liquid natural gas, CNG: Compressed Natural Gas) • Petroleum: Gasoline, Kerosene, Diesel, Fuel Oil , Liquid Petroleum Gas (LPG)
Fuel Approx. single Hydrocarbon Gasoline ~ Octane (C8H18) Diesel ~ Dodecane (C12H26) Methanol ~ Methyl Alcohol (CH3 OH) Natural gas~ Methane (CH4)

Combustion Air
• Combustion is a chemical reaction during which a fuel is oxidized and a large quantity of energy is released. • Oxidizer = Oxygen • Commonly AIR is used as oxidizer (free) • By volume: AIR = 21% O2 + 79% N2 • Therefore, 1 mole of O2 Æ N2 = 79/21 = 3.76 mole
1 kmol O2 + 3.76 kmol N2 = 4.76 kmol of Air Assumption at normal combustion : • N2 absolutely inert (no reaction) • Water is also inert

2

Combustion 1 kmol C + 1 kmol O2 Æ 1 kmol of CO2 C + O2 Reactants Æ CO2 Products (15.3) 3 . AF = mair/mfuel (15.2) To have combustion reaction. it must: • T > ignition temp • Fuel : air ratio must proper • To get good combustion Æ 3T – Temperature (high) – Turbulent (good mixing between fuel and air) – Time (enough to reach complete combustion) •Balancing of chemical reaction: Conservation of mass principle • Air fuel ratio.

H2O. Assuming the products contain only CO2. AF = mair/mfuel = (NM)air/(NM)fuel = 24. and N2. Solution Chemical reaction equation: C8H18 +20 (O2 + 3.Example 15.5 N2: 20*3. determine the mole number of each gas in the products and the airfuel ratio for this combustion process.2 kg air/kg fuel Theoretical and Actual Combustion Processes Complete combustion: 1) all C burns to CO2. • Æ no unburned and no O2 left in products • = Chemically correct amount of air or 100% theoretical air 4 . 3) Dissociation Stoichiometric Air or Theoretical Air: • = minimum amount of air needed for complete combustion.76 N2) Æ xCO2 + yH2O + zO2 + wN2 Balance of each element : @ ReactantS = @ ProductS C: 8=x Æ x =8 Æy=9 H: 18 = 2y O: (20x2) = 2x +y + 2z Æ z = 7. O2.76 = w Æ w = 75.2 Air Fuel Ratio. and 2) all HC burns to H2O Incomplete combustion: combustion Products contains Unburned fuel or components สาเหตุหลัก: 1)Insufficient O2 2) Insufficient mixing.1 Balancing the combustion equation One kmol of octane (C8H18) is burned with air that contains 20 kmol of O2.

76N2) Æ CO2 + 2H2O + 7. ex CH4 + 2(O2 + 3.52N2 Actual combustion processes: need excess air to complete combustion % Excess air: = % more air needed than theoretical air 80% excess air = 180% theoretical air Deficiency of air: = amount of air used < theoretical air (10% deficiency of air = 90% theoretical air) Theoretical and Actual Combustion Processes Equivalent Ratio = (AFactual)/(AFstoich) การประเมิน/ตรวจสอบความสมบูรณของการการเผาไหม Orsat Gas Analyzer = อุปกรณวิเคราะหองคประกอบของ combustion gas (products) ปจจุบันไมคอยนิยมใชแลว – ใช gas analyzer 5 .Theoretical and Actual Combustion Processes Stoichiometric Combustion or Theoretical Combustion: • Complete combustion with 100% theoretical air .

96 kPa Æ Tdp = 52.49 kmol)(100 kPa) Pv = 13.76)aN2 From O2: 1.Example 15.2a = 2+ 3/2+0.2 dew point temperature of combustion products Ethane (C2H6) is burned with 20% excess air during combustion process.2a (O2 + 3.2x4.2a then a = 3.2(O2 + 3. Solution (a) write the chemical reaction equation at 120% theoretical air C2H6 +1.76 kmol)(29 kg/kmol)/[(2kmolx12 kg/kmol)x(3 kmol x 2 kg/kmol)] = 19.7O2 + 15. Assuming complete combustion and a total pressure of 100 kPa.5 C2H6 +4.76 N2) Æ 2CO2 + 3H2O + 0.7O2 + 15.79N2 Air Fuel Ratio.2x3.76 N2)Æ2CO2 + 3H2O + 0.3 oC 6 .76 N2) Æ 2CO2 + 3H2O + 0.3 kg air/kg fuel C2H6 +4.79N2 (b) Tdp = Tsat @ Pv (H2O) Ideal gas mixture Pi/Pm = Ni/Nm Pv = (3 kmol/21.2(O2 + 3. determine (a) the air fuel ratio and (b) the dew point temperature of the products.2aO2 +(1. AF = mair/mfuel = (NM)air/(NM)fuel = (4.

9 oC 7 .72CH4 +0. 1 atm.3 1.3 combustion of gasous fuel with moist air A certain natural gas has the following volumetric analysis: 72% CH4 . Solution 0. moles of air per kmol of fuel can be determined 3.Example 15.88 kPa Æ Tdp = 60. then extra moles water vapor (20%RH at inlet conditions) can be calculated 4. 14%N2 . and 80%RH.09H2+ 0. 2%O2 and 3%CO2. The gases is now burn with stochiometic amount of air that enters combustion chamber at 20oC. Tdp = Tsat @ Pv (H2O) (Ideal gas mixture Pi/Pm = Ni/Nm) Pv = 20.02O2 + 0.14N2 +0. 5. 9% H2 . N of each component in products are known 6. determine the dew point temperature of the products. Rewrite the chemical reaction by adding the water vapor into both side. Assume complete combustion and a total pressure of 1 atm. write the chemical reaction equation at 100% theoretical air (use dry air) 2.76N2)+ xCO2 + yH2O+zN2 Example 15.03CO2 Æ ath(O2+3.

energy is conserved. All of these forms must balance out in the reactants and products to give the system a net energy of zero. some chemical bonds that bind the atoms into molecules are broken and new ones are formed.520 kJ 1 kmol C at 25oC. 1 atm Chamber 1 kmol O2 at 25oC. and nuclear energy. 1 atm 241.Chemical Energy from Process This session deal with the chemical energy within the molecules of a closed system that involve a chemical reaction. 1 atm Combustion Chamber 1 kmol O2 at 25oC. The chemical energy associated with this process is usually different for the reactants and products. Which means that energy cannot be created nor destroyed. During a chemical reaction. 8 . Meaning: ∆Esys = 0 and ∆Eproducts = -∆Ereactants The molecules of a closed system possess energy in various forms such as sensible and latent energy. but it can only change forms. 393. 1 atm First Law of Thermodynamics The first law of thermodynamics states that in any closed system. 1 atm CO2 at 25oC.820 kJ H2O (g) Combustion at 25oC. 1 atm 1 kmol H at 25oC. chemical energy.

atm. which are 25oC and 1 atm. under standard conditions. chemists use the defined equation: ∆H = Σ∆Hf (products) . In order to put the calculation into algebraic form. The defined equation above. Standard Reference State Since composition of a system at the end of a process is no longer the same as that at the beginning of the process. becomes: ∆H° = Σ∆H°f(products) . The superscript “°” is used to indicate property values at the standard state.Enthalpy Change Enthalpy is the system we use to measure that change in energy of a closed system due to chemical bonds being broken. Reaction enthalpies are real physical quantities for which numeric values can be calculated or measured. This standard condition is called the standard reference point. is always calculated as the sum of the enthalpies of the products minus the sum of the enthalpies of the reactants. which is the enthalpy change that occurs in the reaction. there’s a need to use a standard condition in which to make the measurements from.Σ∆Hf (reactants) The reaction enthalpy.Σ∆H°f(reactants) 9 .

76aN2 Balance of oxygen : get a = 12. The calculation for an enthalpy of combustion is done for 1 kmol (1 kg) of fuel is burned completely at a specified temperature and pressure and can be expressed: hc = Hprod – Hreact Example 15. using enthalpy-of-formation data from table A-26. Write chemical reaction equation based on 1 kmol of octane C8H18 +a(O2 + 3. Assume the water in the products is in the liquid form. Energy analysis hC = HP – HR o HR = ∑N hf . Solution 1.R = (Nhf)C8H18 o _ _ _ _ _ o o o ( Nh ( Nh ) HP = ∑N hf = + .P f)H2O f CO2 10 .5 2.Enthalpy of Combustion The enthalpy of reaction in a combustion process is called the enthalpy of combustion (symbolized by hc).76 N2) Æ 8 CO2 + 9H2O(l) + 3.5 Evaluation of the Enthalpy of Combustion Determine the enthalpy of combustion of liquid octane (C8H18) at 25oC and 1 atm.

520 kJ/kmol kJ/kmol hf .Table AA-26 Enthalpy of Formation _ o = -393.CO _ o = -285.C8H18 Enthalpy of combustion = .5.830 kJ/kmol kJ/kmol hf .891 kJ/kg C8H18 Disscussion: This is the HHV of liquid C8H18 in Table A-27 Enthalpy of formation has 2 values : 1.950 kJ/kmol kJ/kmol ho 2 f . for liquid vapor phase -the different = laten heat of vaporization 11 .249.471.100 kJ/kmol C8H18 = -47.H2O _ = . for vapor vapor phase 2.

The property values are obtained by first assigning all of the elements in its chemically stable form at the standard reference state a value of zero (such N2. state Enthalpy of Formation of CO2 = . elements @ ref. This property makes analyzing easier because it represents chemical energy of an element or a compound at the standard reference state. Enthalpy of Formation So we can use this concept to find the enthalpy of formation of individual compounds by adding up the enthalpy for each reaction it takes to react some of the chemically stable elements to get the compound.Enthalpy of Formation The enthalpy of formation is defined as the enthalpy of a substance at a specified state due to its chemical composition. 1 atm. •Consider the formation of CO2 (a compound) from elements C and O2 at 25 oC. O2.393.393. N2.520 kJ HR = 0 . during SSSF process 1st law: Qcv + ΣHi = ΣHe Qcv = HP – HR Qcv = .520 kJ/kmol 12 . C).

13 . HHV.7) m = mass fo water in the products per unit mass of fuel hfg = the enthalpy of vaporization of water at the specified temp.Heating Value of Fuel = the amount of heat released when a fuel is burned completely in SSSF process and the products returned to the state of the reactants….: H2O in products is in LIQUID form Lower heating value. LHV. = absolute value of the enthalpy of combustion of the fuel: Heating value = |hC| kJ/kg fuel Higher heating value..: H2O in products is in Vapor form HHV = LHV + (mhfg)H2O (15.

....(15.. ∆PE~0 Qcv + Σ n i h i = Wcv + Σ n e h e ...9) per unit mole eqn......15......) from Then or U = H − PV o U = N{h o f + ( h − h )} − PV o U = N{h o f + ( h − h ) − P v}..... ∆PE~0 Q12 = W12 + (U 2 − U1 ) Q12 = W12 + (U Pr od − U Re act )...... (i = Reactants.... (15 ...11) _ _ Closed System Æ ∆KE~0...(15 ..(15...ΣN i h i = H Pr od − H Ract .(15 ..4 First Law Analysis of Reacting System SSSF Process: (see Chapter 4 the first law) Æ ∆KE~0.. 1 atm) Qcv − Wcv = ΣN e h e ..) _ _ _ _ _ _ _ _ Q there is no u o f Provided in tables 14 .... and e = Products) where h = h o f + ∆ h T →To o h = ho f + (h− h ) _ _ _ _ _ _ _ _ _ o o _ o o _ (scrip o stand for reference state which is 25o C . Qcv + ΣN i h i = Wcv + ΣN e h e ...8) per rate of mole eqn.

500 K.fuelAF = (0.Example 15. If the exit temperature of the combustion gases is 1. An analysis of the combustion gases reveals that all the hydrogen in the fuel burns to H2O but only 90% of carbon burns to CO2.05 kg fuel/min)(25.Stochiometic combustion equation based on 1 kmol of propane C3H8 (l)+a(O2 + 3. Write chemical reaction equation based on 1 kmol of propane 1. = 25.2*5)(O2 + 3. Solution: Concepts 1.18 kg air/min Answer 15 .65O2 + 4H2O + 28.76 N2) Æ 3CO2 + 4H2O + 3.9*3)CO2 + (0. determine (a) the mass flow rate of the air and (b) the rate of heat transfer from the combustion chamber.9*3)CO (0. mdot.76 N2) Æ (0.53 kg air/kg fuel mass flow rate of air.53 kg air/kg fuel) = 1.1 Theoretical Air-Fuel ratio (Stochiometic) 1. Energy balance: SSSF Q = HP – HR .150% theoretical air combustion equation based on 1 kmol of propane with 90%CÆCO2 + 10%CÆCO C3H8 (l)+(1.1*3)CO + 2.05 kg/min where it is mixed and burned with 50% excess air that enters the combustion chamber at 7oC.76aN2 Balance of oxygen : get a = 5 . with the remaining 10% forming CO.2 with 150% theoretical air + incomplete burned CO Æ AF Æ mass flow rate of air 2.2N2 (a) AF = mair/mfuel = (NM)air/(NM)fuel = ………………. as shown in the figure.6 First Law Analysis of Steady-Flow Combustion Liquid propane (C3H8) enters a combustion chamber at 25oC at a rate of 0.air = mdot.

241. If the final temperature is 1. Solution: Concepts 1.880 kJ/kmol fuel Æ 8. The contents of the tank are ignited. Write chemical reaction equation Assume ideal gas for both reactants and products: Æ PV = NRuT Æ P2 2.393. _ _ _ _ _ _ _ _ _ _ _ (h o = h 298K ) h 280K NA 8.682 8. and e = Products.141 NA NA NA h1500K NA 49.904 9.073 57.364 8.078 47.000K.669 _ (kJ/kmol) (kJ/kmol) (kJ/kmol) (kJ/kmol) .520 . determine (a) the final pressure in the tank and (b) the heat transfer during this process.7 First Law Analysis of Combustion in a Bomb Constant volume tank contains 1 kmol of methane (CH4) gas and 3 kmol of O2 at 25oC and 1 atm. Energy balance: SSSF Q = UP – UR = (Hp-PPV) .Qcv + ΣN i h i = Wcv + ΣN e h e (i = Reactants.530 _ o Remark : h o f ( g ) = h f (l ) + h fg Substitute. Qcv = 363.517 _ _ _ Assume air and combustion gases are ideal gases. and the methane gas burns completely.292 47.999 71.110.910 0 0 . Wcv = 0) Qcv = ΣN e h e − ΣN i h i where o h = ho f + ( h − h ). get data from the property tables ho f Substance C3 H 8 (l ) O2 N2 H 2O( g ) CO2 CO _ h 298K 0 8.118.270 kJ/kg fuel Æ Qdot = mdotQ = 6.820 .89 kW Example 15.669 9.(HR-PRV) 16 .150 8.

ho substitute in equation above .(a) Combustion equation: CH4 (g)+ 3O2 Æ CO2 + 2H2O + O2 Nreact = 1 + 3 = 4 kmol..000K/298K)(1atm) = 3. Nreact = 1 + 2 + 1 = 4 kmol.850 kJ/kg CH 4 Answer 17 .590 kJ/kmol CH 4 or = 717. Æ N1 = N2 Assume ideal gas for all gases: State 1 (Reactants) P1V = N1RuT1 (1) P2V = N2RuT2 (2) State 2 (Products) eqn(2)/eqn(1) P2 = (T2 /T1)*P1 = (1.590/16 = 44.> Amount of heat transfer out = .36 atm answer First law : W12 = 0 : from or Q12 = W12 + (U 2 − U 1 ) Q12 = (U Pr od − U Re act ) o U = H − PV = N{h o f + ( h − h )} − PV o U = N{h o f + ( h − h ) − P v} _ _ _ _ _ _ _ _ Ideal gas P v = Ru T then U= _ _ _ o N{h f + (h− h o ) − Ru T } of each gas and h at each state _ from property tables get valus of _ _ o h f .Q12 = 717.

Solving by trialvalues…and trial-andand-error technique by assume a value of TP get values… substitute in (2) …. • When/how to interporate Error T c Tc ratio rpo n T2 Ta Tb T2 Tc E2 -Ea -Eb 0...∆KE=∆PE=0 : _ _ _ Qcv + ΣN i h i = Wcv + ΣN e h e ΣN i h i = ΣN e h e _ _ o ΣN R {h f + (h− h o )}R _ _ _ o = ΣN P {h f + (h− h o )}P _ _ 1st law To Calculate the adiabatic flame temperature.LHS = RHS . TP 1. Write the combustion equation 2. • How about the 3rd.15..5 Adiabatic Flame Temperature Adiabatic Flame Temperature = Maximum limit of combustion gas temperature of each Air – Fuel mixture (Adiabatic Flame Temperature = Combustion Temperature) Æ Qcv=0.0 +Ec T2 b Inte Tb a 8 -Eb E=0 T2 = 342 oC Ta mi =1..263 kg +Ec -Ea Error 18 ...if not try new TP …. (in good procedure we can interporate the former value to get the right value of TP Trail and error procedure LHS . Apply energy balance (1st law) 3.RHS = • What is your first guess of T • What should be the 2nd trial.Wcv=0 . 4th .

and it is burns with air that enters the combustion chamber at the same state. Adiabatic 3. Determine the adiabatic flame temperature for (a) complete combustion at 100% theoretical air.76 N2) Æ 8 CO2 + 9H2O + 47N2 at TR = 298K at TP = ? 2. ∆KE=∆PE=0 5. No work 4. (b) complete combustion at 400% theoretical air and (c) incomplete combustion (some CO in the products) with 90% theoretical air. Energy balance: HR = HP Qcv + ΣN i h i = Wcv + ΣN e h e ΣN i h i = ΣN e h e _ _ _ _ o o o ΣN R {h o f + ( h − h )}R = ΣN P {h f + ( h − h )}P _ _ _ _ _ _ Q reactants are at reference state (h − h ) R = 0 o o ΣN R {h o f }R = ΣN P {h f + ( h − h )}P _ _ _ _ _ _ o 19 . Combustion equation equation based on 1 kmol of octane C8H18 +12. as shown in the figure. Air and combustion gases are ideal gas 1.8 Adiabatic Flame Temperature in Steady Combustion Liquid octane (C8H18) enters the combustion chamber of a gas turbine steadily at 1 atm and 25oC. Asumptions: 1.5(O2 + 3.Example 15. SSSF process 2.

5 and b = 2.5(O2 + 3. 4th .0x12.236K …………………….5 by trial and error of TP Adiabatic flame temperature = 2..(b) 400% theoretical air : combustion equation:-.263 kg +Ec -Ea Error 20 .RHS = • What is your first guess of T • What should be the 2nd trial. • When/how to interporate Error T c Tc ratio rpo n T2 Ta Tb T2 Tc E2 -Ea -Eb 0..76 N2) Æ 8CO2 + 9H2O + (3.answer C8H18 +4. Combustion equation equation based on 1 kmol of octane at TR = 298K at TP = ? by trial and error of TP Adiabatic flame temperature = 962 K ……………………...5)O2 + 4..answer C8H18 +0.76 N2) Æ aCO2 +bCO + 9H2O + 0.5(O2 + 3..9x47N2 Trail and error procedure LHS .0x47N2 (C) 90% theoretical air : combustion equation:-.0x12.0 +Ec T2 b Inte Tb a 8 -Eb E=0 T2 = 342 oC Ta mi =1. Combustion equation equation based on 1 kmol of octane at TR = 298K at TP = ? C and O balance Æ a = 5. • How about the 3rd.9x12..

669)}N 2 _ _ _ _ (a) Adiabatic flame temperature = 2..393....904)}H 2O + {47(0 + h − 8...241. ..530 = _ h 298K 0 8....820) + h − 9.......520 ........ _ h yyyyK NA ... ...answer 21 ... ... ........395 K ……………….......... ......520) + h − 9..... .950 0 0 ..........364) CO2 + {9(−241.. _ (kJ/kmol) (kJ/kmol) (kJ/kmol) (kJ/kmol) _ Remark : h o f (g) _ _ _ ho f (l ) + h fg _ _ _ o o ΣN R {h o f }R = ΣN P {h f + ( h − h )}P o o o o o o ( Nh o f ) C8 H18 = {N ( h f + h − h )}CO2 + {N ( h f + h − h )}H 2O + {N ( h f + h − h )} N 2 _ _ _ _ _ _ _ _ _ _ 1x(−249..820 ........669 _ h xxxxK NA ..249....904 9.........669 9... ...... .Assume air and combustion gases are ideal gases.....110.....950) = {8(−393...364 8........ get data from the property tables ho f Substance C8 H18 (l ) O2 N2 H 2O( g ) CO2 CO .682 8...

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