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Module 4 - Energy

Prof Russell Howe School of Chemistry, UNSW

Earth Metals Water


Module 4 - ENERGY Overall content of this module

s s s s Photosynthesis: light energy vs chemical energy Coal, petroleum and natural gas Carbon: allotropes and bonding n-alkanes: properties, dispersion forces and their consequences. Distillation. s Energy changes in chemical reactions s Combustion and pollution s Reaction kinetics and catalysis

Energy : General Chemistry Concepts

s Atomic structure: carbon and carbon allotropes s Bonding: bond energies, single, double and triple bonds s Intermolecular forces: dispersion forces and their consequences s Chemical reactions: energetics and energy profiles s Chemical reactions: factors affecting reaction rates s Carbon chemistry: classification of carbon compounds, alkanes, alkenes, alkynes, carbohydrates s Thermodynamics: heats of reaction, combustion s Environmental chemistry: fossil fuels, pollution from combustion s Biological chemistry: photosynthesis

Energy - Relationship to Other Modules

s Energy uses the following concepts from the Earth,Metals and Water Modules s EARTH
q q q q Introduction to bonding and Lewis dot structures light, heat and electricity as common forms of energy bond energies physical vs chemical change, including boiling (and presumably other changes of state)

q organisation of the periodic table,the mole

q intermolecular forces q distillation q endothermic and exothermic reactions

Relationship with the Old Syllabus

s Core 1-atoms and elements
q concept of a chemical element q allotropy

s Core 2- compounds
q systems of formulae and nomenclature

s Core 5-chemical reactions

q equations as useful representations of chemical change q chemical reactions vary in many ways (endo-or exothermic, reaction rates)

s Core 7-energy
q chemicals as energy, H, chemical energy and people

s Core 8-structure and bonding

q arrangement of electrons in atoms (carbon) q covalent bonds q intermolecular forces

Relationship with the Old Syllabus(2)

s Core 11-carbon chemistry
q IUPAC nomenclature (alkanes, alkenes, alkynes, structural formulae) q Hydrocarbons, structure and physical properties, industrial and domestic use, safely precautions q suggested experience: distillation

s Elective 1-chemical energy

q chemicals as fuels: heats of combustion, ignition and flashpoint, volatility, hydrocarbon fuels, safety aspects q enthalpy, standard enthalpy changes, enthalpy of combustion, bond energies

s Elective 3-biological chemistry

q composition of simple monosaccharides and disaccharides q photosynthesis

s Elective 4-chemistry and the environment

q the atmosphere (effects of industrial effluents)

General perspective on ENERGY as a context

s attempts to link together thermodynamics, carbon chemistry, and reaction kinetics, using fuels and combustion as the context s many concepts recurr in the 5 different sub-modules (e.g. bond energies) s some artificial separation of concepts (e.g. carbon chemistry, carbohydrates encountered before simple alkanes, intermolecular forces, only dispersion forces covered in this module)

Living organisms make high energy compounds(1)

s Recall role of photosynthesis in ecosystems s Photosynthesis controls oxygen levels in the atmosphere, and synthesizes carbohydrates s Web resources on photosynthesis
s http://photoscience.la.asu.edu/photosyn/education/photointro.html

s tutorial on photosynthesis
s http://www.life.uiuc.edu/cheeseman/JC.software.html

s photosynthesis tutorial program (PC version is currently free, 1.36Mb) s note that both of these sites give much more detail than is required at this point

Photosynthesis: essential features

s Carbonated water converted to sugar plus oxygen s Overall: 6 H2O + 6 CO2 + 48 photons C6H12O6 + 6 O2 s With the level of chemistry background that students have at this point, this is probably as far as you should go
q One step further is to describe photosynthesis as the oxidation of water by light: q 12H2O + light 6 O2 + 24 H+ + 24 eq followed by fixation of carbon (which does not directly require light) q 6 CO2 + 24 H+ + 24 e- C6H12O6 + 6 H2O

s carbon fixation involves ATP and NADPH, regenerates ADP and NADP. These concepts will recur in the year 12 Biochemistry Option

Living organisms make high energy compounds(2)

s The role of photosynthesis in transforming light energy to chemical energy s relate light energy to wavelength and frequency (concepts of colour, wavelength, photons). Energy content of one mole of photons of different wavelengths?
q Note that the syllabus does not require this, but it may be a useful thing for better students to consider (see next page)

s Role of the production of high energy carbohydrates from carbon dioxide as the important step in the stabilization of the suns energy in usable form s what is a high energy compound? s Combustion as an exothermic process releasing energy s C6H12O6 + 6O2 6CO2 + 6H2O

Energy content of 1 mole of photons

for 1 photon: E = h = hc/ h = 6.626 x 10-34 Js for 1 mole of photons: E = 0.119/ ( /m) J mol-1
colour red orange yellow green blue Wavelength/ nm 650 600 570 530 470

c = 3 x 108 m s-1

Energy/ kJ mol-1 183 198 209 225 253

Living organisms make high energy compounds(3)

s High energy carbohydrates- which ones? s Structural formulae of simple mono, di and polysaccharides (from old syllabus (elective 3, biological chemistry): glucose, fructose, sucrose, starch. Probably only need glucose at this point; the others will appear in Year 12. s Reinforce concept of bond energies; thus need to know structural formulae. s Qualitatively, describe energy release on combustion of glucose as difference between energy required to break bonds and energy released on forming bonds in
q C6H12O6 + 6O2 6CO2 + 6H2O

s Quantitatively, bond energies can be used to estimate this, (next page) but syllabus does not require such calculations

Living organisms make high energy compounds(4)

s Combustion of glucose involves breaking 6 O=O bonds, 7 CH bonds, 5 C-O bonds, 5 O-H bonds, 5 C-C bonds and 1 C=O bond, and forming 12 C=O bonds and 12 O-H bonds s amount of energy released can be estimated from average bond energies s definition: bond energy = enthalpy change on breaking a particular chemical bond (note sign!) s O=O 498 C-H 414 C-O 358 O-H 463 C=O 804 C-C 346 kJ mol-1 (SI Chemical data) s thus net energy release from combusting one mole of glucose is difference between bond energies of bonds formed and bond broken: 2679 kJ s experimental value = 2800 kJ why the difference?

Living organisms make high energy compounds(5)

s Conversely, forming 1 mole of glucose from CO2 and H2O requires 2679 kJ, obtained from sunlight. s Relate energy content of glucose to typical energy consumptions (Selinger, Chemistry in the Market Place) s e.g. average adult woman requires 9 MJ per day s other high energy products of photosynthesis ? s Compare energy contents of glucose with other foods
q q q q q glucose: 15.6 kJ g-1 sucrose: 16.2 brown rice: 14.9 vegetable oil: 37.0 butter: 30

Living organisms make high energy compounds(6)

s Identify the photosynthetic origins of the chemical energy in coal, petroleum and natural gas s describe coal, petroleum and natural gas as naturally synthesized fuels resulting from geological processes. s Chemical structure of coal (typical!!), petroleum, natural gas s Coal information:
s http://www.newcastle.edu.au/department/gl/cfkd/undp.htm#physicochemical s http://www.isr.gov.au/resources/coal_vl/education.html

s natural gas site

s http://www.gsenergy.com.au/energy/school/gas/index.htm s see also Australian Institute of Petroleum site : http://www.aip.com.au/education/index.html

Living organisms make high energy compounds(7)

s What are the energy contents of typical coal, oil and gas molecules? s Compare enthalpy of combustion per gram of carbon, octane and methane s How are coal, oil and gas formed? s Where are the Australian coal, oil and gas reserves, and what is their extent? s Build into student assignments rather than teach directly

There is a wide variety of carbon compounds(1)

s Identify the position of carbon in the periodic table and describe its electronic configuration s describe the allotropes of carbon and relate their physical properties to their atomic arrangement s identify that carbon can form single, double or triple bonds with other carbon atoms s diamond, graphite, fullerenes s three dimensional covalent network versus two dimensional layers versus discrete clusters s tetrahedral versus trigonal versus linear bonding

There is a wide variety of carbon compounds(2)

s Web sites:
q http://www.bris.ac.uk/Depts/Chemistry/MOTM/diamond/diamond.htm q http://www.bris.ac.uk/Depts/Chemistry/MOTM/buckyball/c60a.htm q http://sbchem.sunysb.edu/msl/fullerene.html

s Explain the relationship between carbons combining power and ability to form a variety of bonds and the existence of a large number of carbon compounds
q q q q C-C,C=C,CC, C-H C-O, C=O C-N, C=N, CN C-X

s give a few examples of compounds (IUPAC nomenclature); note that other organic compounds will be met in year12

There is a wide variety of carbon compounds(2A)

s Additional web sites: s http://www.science.org.au/nova/
q buckyballs-a new sphere of science q activities: q is carbon hard or soft q the geometry of the buckyball q how hard is diamond

A variety of carbon compounds are extracted from organic sources(1)

s identify and use the nomenclature for describing straight chained hydrocarbons from C1 to C8 s compare and contrast their properties : which ones? Melting point, boiling point, volatility, viscosity.
q Need to define these properties (refer back to WATER and CHEMICAL EARTH)

s explain the relationship between melting point etc of the above hydrocarbons and their non-polar nature and intermolecular forces (dispersion forces)
q dispersion (London) forces come from instantaneous dipoles, which depend on polarizability q polarizability is not mentioned in the syllabus so should probably not be used, but the size of the instantaneous dipoles depends on number of electrons and the effective volume in which they are confined, thus dispersion forces depend on size of molecule q recall dipoles and dipole dipole interactions from WATER

Supplementary data: n alkanes

Carbon number 1 2 3 4 5 6 7 8 Water Melting point/ K 90 89 85 135 143 178 182 216 273 Boiling point/ K 112 184 231 272.5 309 342 371 399 373 Hvaporization/ Viscosity/ 10-3 kg kJ mol-1 sec-1m-1 8 15 19 22 27 32 37 42 50 0.289 0.401 0.524 0.706 1.00

A variety of carbon compounds are extracted from organic sources(2)

s s s s s s dispersion forces also depend on shape of molecule e.g. methane BP = -162C, n-pentane = 36C, 2,2-dimethylpropane = 10C compare also dispersion forces with dipole-dipole forces e.g. butane, BP = -0.5C, 2-propanone(acetone) = 56C compare magnitudes of dispersion forces with dipole:dipole and hydrogen bonding
q this needs to be done with care. Dispersion forces are present in all atoms and molecules; energy range from 0.05 to 40 kJ mol -1 . Dipole:dipole forces depend on size of molecular dipoles; energy range 5-25 kJ mol -1 . Hydrogen bonding spans a wide range of energies from below 10 to 40 kJ mol -1

s viscosity is another useful illustration of intermolecular forces

A variety of carbon compounds are extracted from organic sources(3)

s describe the use of fractional distillation to separate the components of petroleum and identify the relative amounts and uses of each fraction obtained s e.g. Selinger, Chemistry of the Car s differences between CNG, LPG, petrol, diesel, jet fuel (kerosine), lubricating oil s assess the safety issues associated with storage and use of hydrocarbons in view of their weak intermolecular forces s compare volatility, flash point, ignition temperature, flammability limits (this anticipates combustion)

Supplementary data: combustion hazards

Fuel VP at RT / bar Flash point / C Ignition point/ C -187.7 Explos. Limits/ v% 5-15


















Combustion provides another opportunity to examine the conditions under which chemical reactions occur(1)
s Identify combustion as an exothermic chemical reaction
q reinforce exothermic versus endothermic reactions

s outline changes in molecules during chemical reactions in terms of bond breaking and bond making s explain that energy is required to break bonds..
q reinforce concepts from photosynthesis

s identify the role of a wick and explain the conditions under which it is needed
q this appears to be familiar material from the old syllabus

s this section largely repeats what was covered under Living organisms make high energy compounds

Combustion provides another opportunity to examine the conditions under which chemical reactions occur(2)
s Describe the energy needed to begin a chemical reaction as activation energy s molecular description: reactant molecules must collide with a minimum amount of energy for reaction to occur s Describe the energy profile diagram for both endothermic and exothermic reactions s examples:
q CO + NO2 CO2 + NO E = 134 kJ, H = -226 kJ q 2 HI H2 + I2 E = 180 kJ, H = 159 kJ

Combustion provides another opportunity to examine the conditions under which chemical reactions occur(3)
s explain the relationship between ignition temperature and activation energy s initiation of free radical reactions (C-H bond breaking) requires collisional activation; note that C-H bonds become weaker in longer chain alkanes (compare methane, 435 kJ mol -1 and ethane, 410 kJ mol -1) s identify the sources of pollution which accompany combustion of organic compounds and explain how these can be avoided s describe chemical reactions to summarize examples of complete and incomplete combustion s pollutants: CO2,CO, NO2 (SO2)

Combustion provides another opportunity to examine the conditions under which chemical reactions occur(4)
s s s s s CH4 + 1.5 O2 CO + 2H2O CH4 + 2 O2 CO2 + 2H2O N2 + O2 2 NO NO + 0.5 O2 NO2 (NO produced above 1300C)

s How to reduce pollution of the atmosphere?

q Ensure complete combustion q lower combustion temperature (add combustion catalyst) q catalytic treatment of exhaust gases (this introduces catalysis, which strictly speaking shouldnt happen until the next topic!)

Combustion provides another opportunity to examine the conditions under which chemical reactions occur(5)
s Examples of exhaust gas treatment:
q selective catalytic reduction (power stations) q 6NO2 + 8NH3 7N2 + 12H2O (vanadium oxide catalyst) q selective catalytic reduction (car exhaust) q 2CO + 2NO 2CO2 + N2 q 4CO + 2NO2 4CO2 + N2 q CH4 + 2NO2 CO2 + 2H2O + N2

(Pd/Pt/Rh catalysts)

q role of catalyst is to accelerate desired reactions (leads into next topic)

The extent and rate of energy release are affected by factors..(1)

s Describe combustion in terms of slow, spontaneous and explosive reactions, and explain the conditions under which these occur
q At the lowest level, this can be described in terms of the rate of an exothermic reaction. If the reaction is sufficiently slow, combustion will occur in a controlled fashion. If the rate is fast, the heat produced will increase the reaction rate catastrophically, leading to an explosion. q Rates depend on : q nature of reactants q temperature (refer back to activation energy) q concentrations q To go any further, it is necessary to introduce the concept of reaction mechanism: sequence of reaction steps leading to overall reaction (see example on following page)

Example: combustion of hydrogen

q Combustion described in terms of chain mechanism: q initiation q propagation q termination q Relative rates of three steps determine outcome q explosion occurs if reaction rate increases rapidly with increasing temperature

s 2H2 + O2 2H2O

q initiation: H2 + O2 OH + OH q propagation: q H2 + OH H2O + H q O2 + H O + OH q O + H2 OH + H q termination: q H + OH H2O q OH + W WHO wall reactions q rate of propagation versus termination determines overall reaction rate

The extent and rate of energy release are affected by factors..(2)

s Explain the importance of collisions between molecules as a criterion for determining reaction rates s Explain the relationship between temperature and the kinetic energy of particles s molecules must collide before they can react s collision frequency depends on concentration s outcome of collision depends on kinetic energy
q recall concept of activation energy: minimum kinetic energy needed to overcome activation barrier

s concept of distribution of molecular velocities s average kinetic energy proportional to T

The extent and rate of energy release are affected by factors..(3)

s Describe the role of catalysts in chemical reactions, using a named industrial catalyst as an example s Explain a model of the role of catalysts in changing the rate of chemical reaction s Recall reaction profiles: role of catalyst is to provide an alternative reaction path with a lower activation energy. The catalyst participates in the reaction, but is not consumed. s Examples:
q ammonia synthesis q methanol synthesis q oxidative coupling of methane

The extent and rate of energy release are affected by factors..(4)

s Ammonia synthesis: iron catalyst
q q q q q N2 + 3 H2 2 NH3 N2 + 2 Fe 2 Fe-N H2 + 2Fe 2 Fe-H Fe-N + 3 Fe-H NH3 + 4 Fe catalyst provides an alternative pathway by dissociating nitrogen and hydrogen

s Methanol synthesis: copper/zinc oxide catalyst

q q q q q CO + 2 H2 CH3OH CO + Cu Cu-(CO) H2 + ZnO Zn(H)O(H) Cu-(CO) + 2 Zn(H)O(H) CH3OH + 2 ZnO catalyst provides an alternative pathway by activating but not dissociating CO, and dissociating hydrogen

The extent and rate of energy release are affected by factors..(5)

s Oxidative coupling of methane: MgO catalyst (doped with alkali metal)
q q q q q q 2 CH4 + O2 C2H4 + 2 H2O CH4 + MgO CH3 + MgOH 2 CH3 C2H6 C2H6 + 2 MgO C2H4 + 2MgOH 4 MgOH + O2 4 MgO + 2 H2O catalyst provides alternative pathway by breaking C-H bonds

s CSIRO (North Ryde) pilot plant ca 1991, but not economic!!