D. Energy Changes and Rates of Reaction · Energy Changes and Rates of ReactionMaking Reactions More Efficient: Conditions, Catalysts and Sustainability
D1.2 D3.5 D2.5 A1.9 A2.1About 70 minutes
Learning goals- I can explain how temperature, surface area, pressure and catalysts can make combustion, decomposition and neutralization reactions more efficient.
- I can use thermochemical data to calculate the energy gained by a condensing furnace or needed by a lime kiln.
- I can calculate atom economy and use it, with other factors, to judge the sustainability of a process.
- I can describe careers related to improving the efficiency of chemical processes.
Words to know
efficiency
The useful energy (or output) obtained from a process divided by the energy (or input) supplied, often as a percentage.
condensing furnace
A furnace that recovers the energy released when water vapour in the exhaust condenses.
catalytic converter
A device in a vehicle exhaust system that uses metal catalysts to convert harmful gases into less harmful ones.
green chemistry
The design of chemical products and processes that reduce or eliminate hazardous substances and waste.
atom economy
The mass of the desired product divided by the total mass of all products, as a percentage.
sustainability
Meeting present needs without compromising the ability of future generations to meet their needs.
Same reaction, less waste
Industries and households run the same reactions over and over: burning fuels, decomposing limestone, neutralizing acids. Small improvements in how a reaction is run, multiplied by millions of furnaces or thousands of tonnes of product, add up to large savings in energy, money and emissions. In this lesson you will apply what you know about energy changes and rates to judge how conditions such as temperature, pressure, surface area and catalysts can make reactions more efficient (expectation D1.2), and how that connects to sustainability.
Combustion: getting more heat from each mole of fuel
Natural gas (mostly methane) heats most Ontario homes. Look at two thermochemical equations:
CH₄(g) + 2O₂(g) → CO₂(g) + 2H₂O(l) ΔH = −890.3 kJ
CH₄(g) + 2O₂(g) → CO₂(g) + 2H₂O(g) ΔH = −802.3 kJ
The difference, 88.0 kJ, is the energy released when 2 mol of water vapour condense (Hess's law). An older furnace sends hot water vapour up the chimney, wasting that energy. A condensing furnace has a second heat exchanger that cools the exhaust enough for the water to condense, capturing the extra energy. Most new natural-gas furnaces sold in Canada are condensing models, typically rated at about 90% to 98% efficiency.
Other ways to improve combustion efficiency:
- Correct air-to-fuel ratio: too little oxygen gives incomplete combustion (carbon monoxide and soot, less energy); far too much air carries heat away up the chimney.
- Surface area: power plants and cement kilns that burn solid fuels grind them to fine powder so they burn quickly and completely.
- Catalysts: a car's catalytic converter uses metals such as platinum, palladium and rhodium to convert carbon monoxide, unburned hydrocarbons and nitrogen oxides into carbon dioxide, water and nitrogen at exhaust temperatures.
A condensing furnace recovers the energy released when water vapour in the exhaust condenses. The exhaust leaves cool enough to vent through plastic pipe.Worked exampleExample 1: How much does condensing help?
Use the two equations above. (a) What percentage of the energy available from burning methane (forming liquid water) is lost if all the water leaves as vapour? (b) How much extra energy is captured per cubic metre of natural gas, if 1 m³ contains about 41 mol of methane?
- (a) Energy lost = 890.3 − 802.3 = 88.0 kJ per mole of CH₄. Percentage = 88.0 ÷ 890.3 × 100% = 9.88% ≈ 9.9%.
- (b) Extra energy = 41 mol × 88.0 kJ/mol = 3608 kJ ≈ 3.6 MJ per cubic metre (about 3.6 × 10³ kJ).
- Interpretation: capturing the condensation energy alone can raise efficiency by up to about 10 percentage points; real furnaces also lose some heat in other ways.
(a) about 9.9%; (b) about 3.6 × 10³ kJ per cubic metre.
Decomposition: making lime
Lime (calcium oxide) is used to make cement, steel and paper, and to treat water. It is made by heating limestone in a kiln:
CaCO₃(s) → CaO(s) + CO₂(g) ΔH = +178.3 kJ
This reaction is endothermic and very slow at room temperature, so kilns run at about 900 °C or higher. Ways to make it more efficient:
- Temperature: high enough for a fast rate; much hotter only wastes fuel.
- Surface area: crushed limestone of a suitable size decomposes faster than large blocks, but powder that is too fine can block the gas flow through the kiln.
- Removing CO₂: carrying the carbon dioxide away helps the reaction go to completion (you will study why in the Chemical Equilibrium unit).
- Heat recovery: using the hot exhaust gases to preheat the incoming limestone.
Note that the CO₂ released by the reaction itself is a large source of emissions from cement and lime plants, in addition to the CO₂ from the fuel. Researchers are developing ways to capture it.
Worked exampleExample 2: Energy for a tonne of lime
Calculate the minimum energy needed to decompose enough CaCO₃ to make 1.00 t (1.00 × 10⁶ g) of CaO. (M of CaO = 56.08 g/mol.)
- n(CaO) = 1.00 × 10⁶ g ÷ 56.08 g/mol = 1.783 × 10⁴ mol.
- Energy = 1.783 × 10⁴ mol × 178.3 kJ/mol = 3.18 × 10⁶ kJ = 3.18 × 10³ MJ.
- This is the minimum: a real kiln also heats the rock to about 900 °C and loses heat to the surroundings, so it uses considerably more fuel.
about 3.18 × 10⁶ kJ (3.18 GJ) per tonne of lime, at minimum.
Neutralization: restoring acidic land and water
Acid precipitation and mining emissions acidified many lakes and soils in Northern Ontario. Around Sudbury, the regreening program has spread crushed limestone over acidic, metal-contaminated soils since the late 1970s. The limestone neutralizes the acid:
CaCO₃(s) + 2H⁺(aq) → Ca²⁺(aq) + H₂O(l) + CO₂(g)
which allows grass and trees to grow again. Choosing ground limestone (large surface area) makes it react faster, and it is much safer to handle than quicklime or strong bases. In industry, acidic wastewater is neutralized before it is released, and choosing the right base, concentration and mixing rate keeps the process safe and controlled, because neutralization is exothermic.
Catalysts and sustainability
Catalysts lower activation energy, so reactions can run at lower temperatures and pressures, saving energy:
- The Haber process for ammonia (N₂ + 3H₂ ⇌ 2NH₃) uses an iron-based catalyst; the choice of temperature and pressure is a compromise you will study in the Chemical Equilibrium unit. Fertilizer made from this ammonia feeds a large share of the world's population.
- Enzymes in laundry detergents (proteases, lipases and amylases) break down protein, fat and starch stains in cold water. Heating water accounts for much of the energy used in washing clothes, so washing in cold water saves energy.
- Contact-lens cleaning systems use a small platinum-coated disc to catalyse the decomposition of hydrogen peroxide into water and oxygen, so the solution becomes safe to use on the eye within hours.
Green chemistry (a set of twelve principles published by Paul Anastas and John Warner in 1998) encourages chemists to design reactions that use catalysts, run at moderate temperatures and pressures, use safer substances and waste fewer atoms. One measure is atom economy:
atom economy = (mass of desired product ÷ total mass of all products) × 100%
Atom economy for three reactions. Adding water to ethene puts every atom into the product; fermentation and lime-making release CO₂ as a by-product.Worked exampleExample 3: Comparing two routes to ethanol
Ethanol can be made by fermentation, C₆H₁₂O₆ → 2C₂H₅OH + 2CO₂, or by adding water to ethene, C₂H₄ + H₂O → C₂H₅OH. Calculate the atom economy of each and discuss which is more sustainable.
- Fermentation: mass of ethanol = 2 × 46.07 = 92.14 g; total products = 92.14 + 2 × 44.01 = 180.16 g. Atom economy = 92.14 ÷ 180.16 × 100% = 51.1%.
- Ethene hydration: one product only, so atom economy = 100%.
- Discussion: ethene hydration wastes no atoms, but ethene is usually made from fossil fuels, and the reaction needs a catalyst, high temperature and high pressure. Fermentation has a lower atom economy but uses renewable plant sugars at warm temperatures with enzymes (yeast). Sustainability depends on more than one measure: raw materials, energy use, by-products and their uses (the CO₂ from fermentation can be captured and sold).
Fermentation 51.1%; ethene hydration 100%. Neither is simply "better": a full judgement weighs feedstock, energy and by-products.
Just for funA cold-water wash with enzyme detergent is chemistry quietly doing your chores: tiny protein catalysts snip apart grass and gravy stains while the water heater takes the day off.
Careers
Chemical engineers design and optimize industrial processes such as kilns and ammonia plants. Process technologists, often trained at Ontario colleges, monitor and adjust reaction conditions in plants. Energy advisors evaluate homes for efficiency upgrades such as condensing furnaces and heat pumps. Environmental scientists plan and monitor projects such as the Sudbury regreening.
Hands-on activityHome energy audit for reactions
You need: a notebook, and a grown-up to help you look at appliances. Do not open any appliance, gas line or vent.
- Find two places in your home where a chemical reaction or process releases or uses energy (for example a gas furnace or water heater, a gas stove, a car, the clothes dryer, or the dishwasher with its detergent).
- With a grown-up, read the label or manual of one gas appliance and look for its efficiency rating. (On a furnace, a white plastic vent pipe usually means a condensing model.)
- Look at the laundry detergent label. Does it mention enzymes, or say it works in cold water?
- For each item, write one change in conditions (temperature, catalyst, air supply, surface area, timing) that could make the process more efficient, and explain it using collision theory or energy changes.
What to look for: reasons that connect to the chemistry: "A condensing furnace captures the energy from condensing water vapour," or "Enzymes act as catalysts, so the wash works at a lower temperature, saving the energy needed to heat water."
Your turn
1Why does a condensing furnace release more heat per mole of methane than a non-condensing one?
It cools the exhaust so the water vapour condenses, releasing the energy of condensation (88.0 kJ per mole of CH₄) into the house instead of sending it up the chimney.
2What does a catalytic converter do, and what kind of substances act as the catalyst?
It converts CO, unburned hydrocarbons and nitrogen oxides into CO₂, H₂O and N₂. The catalysts are metals such as platinum, palladium and rhodium.
3Why is limestone crushed before it is heated in a kiln?
Crushing increases the surface area, so heat reaches more of the rock and the decomposition happens faster.
4Calculate ΔH for CaCO₃ → CaO + CO₂ from ΔHf values: CaCO₃ −1206.9, CaO −635.1, CO₂ −393.5 kJ/mol.
ΔH = (−635.1 + −393.5) − (−1206.9) = +178.3 kJ.
5How do enzymes in detergents save energy?
They are catalysts that let stains break down quickly in cold water, so less energy is needed to heat the water.
6Calculate the atom economy of making CaO from CaCO₃ (M: CaO 56.08, CO₂ 44.01 g/mol).
56.08 ÷ (56.08 + 44.01) × 100% = 56.0%.
More practice: warm-up
1Name one condition, other than temperature, that can be changed to speed up a reaction.
Any one: surface area, concentration, a catalyst, pressure (for gases).
2Is the decomposition of limestone exothermic or endothermic?
Endothermic (ΔH = +178.3 kJ).
3What gas is produced when limestone neutralizes acid?
4What does a catalyst do to the activation energy?
It lowers it, by providing a different pathway.
The percentage of the total mass of products that is the desired product.
More practice: on your own
1A non-condensing furnace delivers 80% of the 890.3 kJ/mol available and a condensing furnace 95%. How much more energy does the condensing furnace deliver per mole of methane? Explain.
0.95 × 890.3 − 0.80 × 890.3 = 0.15 × 890.3 = 134 kJ per mole more. Part comes from condensing the water vapour (up to 88.0 kJ) and part from transferring more of the remaining heat.
2Explain why running a lime kiln much hotter than needed is not efficient.
The rate is already fast enough; extra temperature burns more fuel and loses more heat to the surroundings without producing much more lime, and it adds CO₂ emissions.
3Why does a gas furnace need the correct air-to-fuel ratio?
Too little air gives incomplete combustion (CO, soot, less energy released per mole of fuel). Too much air absorbs heat and carries it up the exhaust. The right ratio gives complete combustion with the least waste.
4Explain why spreading ground limestone is safer than spreading quicklime (CaO) on acidic soil, using energy changes.
CaO reacts strongly and exothermically with water (and acid), and is caustic, so it can burn skin and harm plants. Ground limestone reacts more gently and slowly with acid, so it is safer and still neutralizes the acid.
5Using ideas from this lesson, explain one way in which catalysts contribute to sustainability.
Catalysts let reactions run at lower temperatures and pressures, which saves fuel and reduces CO₂ emissions; they can also make a reaction more selective, reducing waste by-products. Example: enzymes in cold-water detergents.
Challenge
1Write the thermochemical equations to show that the energy difference between the two methane combustion equations equals the energy of condensing 2 mol of water. ΔH for H₂O(g) → H₂O(l) is −44.0 kJ/mol.
CH₄ + 2O₂ → CO₂ + 2H₂O(g), ΔH = −802.3 kJ. 2H₂O(g) → 2H₂O(l), ΔH = 2 × (−44.0) = −88.0 kJ. Sum (Hess's law): CH₄ + 2O₂ → CO₂ + 2H₂O(l), ΔH = −802.3 + (−88.0) = −890.3 kJ, matching the first equation.
2A cement plant considers burning wood waste instead of coal in its kiln. List two factors, beyond ΔH of combustion, that should be considered, and explain why.
Any two: the energy content per kilogram (wood is lower, so more mass is needed); moisture (energy is wasted evaporating water); net CO₂ emissions over the life cycle (wood may be regrown); other emissions (particulates, NOx, SO₂); supply and cost; the process CO₂ from limestone is unchanged.
3The atom economy for making lime is only 56.0%. Suggest how a lime plant could make the process more sustainable, and explain any limitation.
Capture the CO₂ by-product (carbon capture) and use it (e.g., in greenhouses, carbonated drinks, or to make other chemicals) or store it underground. Limitation: capturing and compressing CO₂ requires energy and money, and uses for CO₂ are limited compared to the amount produced. Also: recover waste heat to reduce fuel use.
Check your understandingQuiz
1. A condensing furnace is more efficient than a non-condensing furnace mainly because it
2. Which change would most directly make a solid fuel burn faster and more completely?
3. The decomposition of limestone, CaCO₃ → CaO + CO₂, has ΔH = +178.3 kJ. Which statement is correct?
4. Enzymes in laundry detergent help save energy because they
5. Making ethanol from ethene and water has an atom economy of 100% because
6. Ground limestone is used to regreen acidic soils near Sudbury. Grinding it
For parents and teachersBig ideas (D1.2): the conditions under which a reaction is run (temperature, surface area, concentration, pressure and catalysts) can be chosen to make common reactions such as combustion, decomposition and neutralization more efficient. Efficiency saves energy and money and reduces emissions, which supports sustainability. Green chemistry and atom economy are tools for judging how sustainable a process is.
How to help: The home audit is a natural conversation. Show your teen the furnace or water heater label, and talk about choices your family makes (cold-water washing, furnace maintenance). Ask them to explain the chemistry behind each choice.
Common difficulties:
- Thinking a catalyst changes ΔH (it changes only the activation energy and the rate).
- Confusing efficiency (useful energy out ÷ energy in) with atom economy (mass of desired product ÷ mass of all products).
- Treating one measure as the whole story: sustainability involves raw materials, energy, by-products and costs.
Activity safety: look at labels only. Never open a furnace, gas line, vent or appliance panel.