CHEMICAL REACTION I am teaching Engineering Thermodynamics to a class of 75 undergraduate students. I plan to go through these slides in one 90-minute lecture. Zhigang Suo, Harvard University Before coming to class, please watch these videos on fuel cells: Video 1: Video 2:

Atom, molecule, and chemical bond 2 hydrogen atom, H nucleus electron nucleus 1-electron cloud hydrogen molecule, H 2 molecule chemical bond nucleus 2-electron cloud nucleus

3 Chemical reaction beaks and reforms chemical bonds destroys and creates molecules conserves the number of atoms in each species H2H2 O2O2 H2OH2O

Plan Fossil-fueled civilization Conservation of mass Conservation of energy Generation of entropy 4

Combustion A fuel and oxygen react, produce other molecules, and release energy by heat. C + O 2  CO 2, heat out 5

6 6

7 Annual Energy Outlook 2015, Prepared by US Energy Information Administration (EIA)

8 Annual Energy Outlook 2014, Prepared by US Energy Information Administration (EIA)

9 Annual Energy Outlook 2015, Prepared by US Energy Information Administration (EIA)

10 Annual Energy Outlook 2015, Prepared by US Energy Information Administration (EIA)

11 On 18 November 2015, the UK energy secretary proposes to close all Britain’s coal- fired power plants by 2025.

12 The Stone Age did not end because humans ran out of stones. It ended because it was time for a re-think about how we live. William McDonough

Plan Fossil-fueled civilization Conservation of mass Conservation of energy Generation of entropy 13

Coal Earliest recognized use: China 4000 BC Industrial Revolution Pollution 14 Composition carbon hydrogen sulfur oxygen nitrogen

15 Petroleum ships, cars, airplanes Rockefeller, Middle East fuelmoleculeformula gasolineoctaneC 8 C 18 diesel fueldodecaneC 12 H 26 Kerosene lamp 煤油灯 Yergin, The Prize, 1991

Natural gas primarily methane, CH

Dry air 17 gasformulamolar mass, kg/kmolnumber fraction nitrogenN2N oxygenO2O argonAr carbon dioxideCO In analyzing combustion, we approximate dry air as 0.21 O 2 and 0.79 N 2 by number fraction. 0.79/0.21 = 3.76 (1 kmol of O 2 ) + (3.76 kmol of N 2 ) = (4.76 kmol of air) Oxygen participates in combustion. Nitrogen does not participates in combustion.

18 All the carbon in the fuel burns to CO 2 All the hydrogen burns to H 2 O All the sulfur (if any) burns to SO 2. Complete combustion

19 Air-fuel ratio m = nM m = mass n = number of moles M = molar mass

20 20 kmol C: H: O: 8 = x 18 = 2y 40 = 2x + y + 2z x = 8 y = 9 z = 7.5 Stoichiometry Chemical reaction conserves the number of atoms in each species.

21 a th kmol C: H: O: 8 = x 18 = 2y 2a th = 2x + y x = 8 y = 9 a th = 12.5 Theoretical air Air containing just right amount of oxygen to complete combustion No excess or deficiency of O 2

22 Excess air Example: 100% excess air = 200% theoretical air 25 kmol Combustion in theoretical air: Theoretical air: Combustion in 100% excess air: Combustion in excess air C: H: O: 8 = x 18 = 2y 50 = 2x + y + 2z x = 8 y = 9 z = 12.5

Plan Fossil-fueled civilization Conservation of mass Conservation of energy Generation of entropy 23

24 Enthalpy of formation formation standard reference state 298K, 1 atm per mole enthalpy Steady-flow combustion chamber O K, 1 atm CO K, 1 atm C 298 K, 1 atm Sign convention Q > o means heat goes from the environment to the chamber C + O 2  CO 2, heat out Q

25 Enthalpy of combustion Steady-flow combustion chamber C 8 H K, 1atm Air 298 K, 1atm H 2 O (l) CO 2 N K, 1atm Q

Enthalpy 26 C + O 2  CO 2 Steady-flow combustion chamber O K, 1 atm CO K, 1 atm C 298 K, 1 atm

27 Steady flow combustion chamber C 8 H K, 1 atm Air 288 K, 1 atm Q H 2 O CO 2 O 2 N K, 1 atm

28 Closed system T 1,P 1 C 8 H 18 + Air Q T 2,P 2 H 2 O CO 2 O 2 N 2 W The Pv terms are negligible for solids and liquids, and can be replaced by R u T for gases that behave as an ideal gas.

29 Calculating the adiabatic flame temperature by hand requires iteration. Adiabatic flame temperature

Plan Fossil-fueled civilization Conservation of mass Conservation of energy Generation of entropy 30

31 The entropy of a component of an ideal-gas mixture depends on the temperature and the partial pressure of the component. P 0 = 1 atm P i = y i P, partial pressure y i number fraction P total pressure of mixture. Entropy is absolute S = log 

32 What you need to know about energy, The National Academies.

Fuel cell uses reaction to generate electricity directly. 33 Video 1: Video 2:

34 When confused, isolate steady-flow combustion chamber T = 25 C 1 atm C 8 H 18 T = 10 C 1 atm air Q T = 1000 K H 2 O CO 2 O 2 N 2 Source, T 0 Isolated system (IS) Energy is additive: Entropy is additive: Isolated system conserves energy over time: Isolated system generates entropy over time: Eliminate Q from the above two expressions: Reversible process generates maximum work (constant P and T in reactants, products, and surroundings): W

35 Reversible work

36 Electrochemistry: Open-circuit voltage

Summary Combustion of fossil fuel may dominate energy market for decades. Conservation of mass. Stoichiometry. Chemical reaction destroys and creases molecules, but conserves the number of atoms in every species. Conservation of energy. Enthalpy of formation. Generation of entropy. Absolute entropy Fuel cell turns reaction directly into electricity, and is not limited by the Carnot efficiency. 37