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Chemical reactions · Types of reactions

Stoichiometry in industrial processes

Before you start, make sure you know: Stoichiometric calculations (Chemistry (high school))
Before you start, make sure you know: Calculations with moles (Chemistry (high school))

A fertilizer plant in the Corn Belt never works with "exact" reactants. An ammonia reactor receives nitrogen and hydrogen in proportions that are never exactly $1:3$; a furnace does not yield the $100\ \%$ that the equation predicts; an iron ore arrives mixed with rock that is of no use at all. Calculating how much product actually comes out of a plant requires combining ideas you may know separately (mole ratio, percent purity and limiting reactant) with one more: percent yield.

Mole ratios in industrial reactions

A plant needs to know how much ammonia it can make from the nitrogen it feeds in. The first step is always the same: the balanced equation gives you the mole ratios.

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A fertilizer plant synthesizes ammonia via the Haber process: $\text{N}2 + 3\ \text{H}2 \rightarrow 2\ \text{NH}3$. a) How many moles of ammonia are obtained, at most,…

A fertilizer plant synthesizes ammonia via the Haber process: $\text{N}_2 + 3\ \text{H}_2 \rightarrow 2\ \text{NH}_3$.

  1. a) How many moles of ammonia are obtained, at most, from $5\ \text{mol}$ of nitrogen?
  2. b) How many moles of hydrogen are consumed in that case?
Solve
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In the blast furnace, the main ore reduction reaction is $\text{Fe}2\text{O}3 + 3\ \text{CO} \rightarrow 2\ \text{Fe} + 3\ \text{CO}2$. a) How many moles of iron are…

In the blast furnace, the main ore reduction reaction is $\text{Fe}_2\text{O}_3 + 3\ \text{CO} \rightarrow 2\ \text{Fe} + 3\ \text{CO}_2$.

  1. a) How many moles of iron are obtained from $2\ \text{mol}$ of iron(III) oxide?
  2. b) Given that $M(\text{Fe}) = 56\ \text{g/mol}$, calculate the mass of iron obtained from $1\ \text{mol}$ of iron(III) oxide.
Solve
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In the manufacture of sulfuric acid, the key stage is the oxidation of sulfur dioxide: $2\ \text{SO}2 + \text{O}2 \rightarrow 2\ \text{SO}3$. a) How many moles of sulfur…

In the manufacture of sulfuric acid, the key stage is the oxidation of sulfur dioxide: $2\ \text{SO}_2 + \text{O}_2 \rightarrow 2\ \text{SO}_3$.

  1. a) How many moles of sulfur trioxide are obtained from $4\ \text{mol}$ of sulfur dioxide?
  2. b) How many moles of oxygen are consumed in that transformation?
Solve

From grams (or kilograms) to product

A scale in a plant reads kilograms, not moles. How do you get from the mass of a reactant going in to the mass of product coming out?

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In the Haber process, $\text{N}2 + 3\ \text{H}2 \rightarrow 2\ \text{NH}3$, the molar masses are $M(\text{N}2) = 28\ \text{g/mol}$, $M(\text{H}2) = 2\ \text{g/mol}$ and…

In the Haber process, $\text{N}_2 + 3\ \text{H}_2 \rightarrow 2\ \text{NH}_3$, the molar masses are $M(\text{N}_2) = 28\ \text{g/mol}$, $M(\text{H}_2) = 2\ \text{g/mol}$ and $M(\text{NH}_3) = 17\ \text{g/mol}$.

  1. a) Calculate the mass of ammonia obtained from $28\ \text{g}$ of nitrogen with sufficient hydrogen.
  2. b) Calculate the mass of hydrogen consumed and check that the law of conservation of mass is satisfied.
Solve
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A cement plant decomposes limestone in its kiln: $\text{CaCO}3 \rightarrow \text{CaO} + \text{CO}2$, with molar masses $M(\text{CaCO}3) = 100\ \text{g/mol}$,…

A cement plant decomposes limestone in its kiln: $\text{CaCO}_3 \rightarrow \text{CaO} + \text{CO}_2$, with molar masses $M(\text{CaCO}_3) = 100\ \text{g/mol}$, $M(\text{CaO}) = 56\ \text{g/mol}$ and $M(\text{CO}_2) = 44\ \text{g/mol}$. $100\ \text{g}$ of pure calcium carbonate is loaded.

  1. a) Calculate the mass of quicklime ($\text{CaO}$) obtained.
  2. b) Calculate the mass of carbon dioxide released.
  3. c) Check that the sum of the masses of the products equals the mass of the reactant.
Solve
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In industry, the kilomole ($1\ \text{kmol} = 1000\ \text{mol}$) is often used: the mass of one kilomole in kilograms is numerically equal to the molar mass in…

In industry, the kilomole ($1\ \text{kmol} = 1000\ \text{mol}$) is often used: the mass of one kilomole in kilograms is numerically equal to the molar mass in $\text{g/mol}$. For the Haber process, $\text{N}_2 + 3\ \text{H}_2 \rightarrow 2\ \text{NH}_3$, we have $M(\text{N}_2) = 28\ \text{kg/kmol}$, $M(\text{H}_2) = 2\ \text{kg/kmol}$ and $M(\text{NH}_3) = 17\ \text{kg/kmol}$. A plant consumes $140\ \text{t}$ of nitrogen per day.

  1. a) Express that mass of nitrogen in kmol.
  2. b) Calculate the metric tons of ammonia that the plant produces per day.
  3. c) Calculate the metric tons of hydrogen it needs daily.
Solve

The limiting reactant in industrial quantities

If you mix $24\ \text{g}$ of magnesium with $32\ \text{g}$ of oxygen to form magnesium oxide, the reaction stops leaving $16\ \text{g}$ of oxygen untouched: why does the process stop dead if one of the reactants is still in the container?

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Industry obtains hydrochloric acid by direct synthesis from the elements: $\text{H}2 + \text{Cl}2 \rightarrow 2\ \text{HCl}$. A reactor is loaded with $3\ \text{mol}$ of…

Industry obtains hydrochloric acid by direct synthesis from the elements: $\text{H}_2 + \text{Cl}_2 \rightarrow 2\ \text{HCl}$. A reactor is loaded with $3\ \text{mol}$ of hydrogen and $2\ \text{mol}$ of chlorine. The reactor feed is represented using the particle model:

reactor 3 mol H₂ 2 mol Cl₂ ?
  1. a) Determine which reactant is the limiting reactant, justifying your answer using stoichiometry.
  2. b) Calculate the moles of $\text{HCl}$ formed.
  3. c) Calculate the moles of excess reactant remaining unreacted and the mass of $\text{HCl}$ obtained ($M(\text{HCl}) = 36.5\ \text{g/mol}$).
Solve
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Titanium for the aerospace industry is obtained via the Kroll process: $\text{TiCl}4 + 2\ \text{Mg} \rightarrow \text{Ti} + 2\ \text{MgCl}2$, with molar masses…

Titanium for the aerospace industry is obtained via the Kroll process: $\text{TiCl}_4 + 2\ \text{Mg} \rightarrow \text{Ti} + 2\ \text{MgCl}_2$, with molar masses $M(\text{TiCl}_4) = 190\ \text{g/mol}$, $M(\text{Mg}) = 24\ \text{g/mol}$ and $M(\text{Ti}) = 48\ \text{g/mol}$. A reactor is loaded with $190\ \text{g}$ of titanium tetrachloride and $36\ \text{g}$ of magnesium.

  1. a) Determine the limiting reactant.
  2. b) Calculate the mass of titanium obtained.
  3. c) Calculate the moles of excess reactant remaining unreacted.
Solve
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A plant wants to produce $480\ \text{kg}$ of titanium via the Kroll process: $\text{TiCl}4 + 2\ \text{Mg} \rightarrow \text{Ti} + 2\ \text{MgCl}2$ (…

A plant wants to produce $480\ \text{kg}$ of titanium via the Kroll process: $\text{TiCl}_4 + 2\ \text{Mg} \rightarrow \text{Ti} + 2\ \text{MgCl}_2$ ($M(\text{TiCl}_4) = 190\ \text{kg/kmol}$; $M(\text{Mg}) = 24\ \text{kg/kmol}$; $M(\text{Ti}) = 48\ \text{kg/kmol}$).

  1. a) Calculate the mass of titanium tetrachloride required.
  2. b) Calculate the theoretical mass of magnesium and the mass that must be loaded if working with an excess of $25\ \%$.
  3. c) Explain why it is advantageous to work with excess magnesium even if it increases the cost of the process, and why the plant subsequently electrolyzes the $\text{MgCl}_2$ obtained to recover the magnesium.
Solve

The yield of a real process

When you heat $100\ \text{g}$ of pure calcium carbonate, stoichiometry predicts exactly $56\ \text{g}$ of quicklime, but in the industrial kiln you collect only $50.4\ \text{g}$: where do the missing grams go if atoms cannot be destroyed?

Comparison between an expected theoretical mass of 100 tonnes and an actual mass obtained of 92 metric tons, which defines a percent yield of 92%. 100 t theoretical 92 t actual yield = 92/100 · 100 = 92 %
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A cement plant calculates that, according to stoichiometry, its kiln should produce $100\ \text{t}$ of lime per day, but the actual production is $92\ \text{t}$. a)…

A cement plant calculates that, according to stoichiometry, its kiln should produce $100\ \text{t}$ of lime per day, but the actual production is $92\ \text{t}$.

  1. a) Calculate the yield of the kiln, as a percentage.
  2. b) State two reasons why a real industrial process might not reach the theoretical yield of $100\ \%$.
Solve
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A lime kiln decomposes $200\ \text{g}$ of pure calcium carbonate: $\text{CaCO}3 \rightarrow \text{CaO} + \text{CO}2$, with $M(\text{CaCO}3) = 100\ \text{g/mol}$ and…

A lime kiln decomposes $200\ \text{g}$ of pure calcium carbonate: $\text{CaCO}_3 \rightarrow \text{CaO} + \text{CO}_2$, with $M(\text{CaCO}_3) = 100\ \text{g/mol}$ and $M(\text{CaO}) = 56\ \text{g/mol}$.

  1. a) Calculate the theoretical mass of quicklime that should be obtained.
  2. b) If the actual yield of the kiln is $90\ \%$, calculate the mass of lime obtained in practice.
  3. c) Suggest a reason why the kiln does not reach the theoretical yield.
Solve
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In the Haber process, $\text{N}2 + 3\ \text{H}2 \rightarrow 2\ \text{NH}3$, only part of the gas is converted on each pass through the reactor. $10\ \text{mol}$ of…

In the Haber process, $\text{N}_2 + 3\ \text{H}_2 \rightarrow 2\ \text{NH}_3$, only part of the gas is converted on each pass through the reactor. $10\ \text{mol}$ of nitrogen is introduced with excess hydrogen, and the conversion per pass is $40\ \%$ ($M(\text{NH}_3) = 17\ \text{g/mol}$).

  1. a) Calculate the theoretical mass of ammonia if all the nitrogen reacted.
  2. b) Calculate the mass of ammonia actually obtained on one pass.
  3. c) Explain what is done industrially with the gas that leaves the reactor unreacted and why this decision improves the overall utilization of nitrogen.
Solve

Combining purity, limiting reactant and yield

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A steel mill receives an iron ore with $80\ \%$ by mass of iron(III) oxide; the rest is inert gangue that does not react. In the blast furnace:…

A steel mill receives an iron ore with $80\ \%$ by mass of iron(III) oxide; the rest is inert gangue that does not react. In the blast furnace: $\text{Fe}_2\text{O}_3 + 3\ \text{CO} \rightarrow 2\ \text{Fe} + 3\ \text{CO}_2$, with $M(\text{Fe}_2\text{O}_3) = 160\ \text{kg/kmol}$ and $M(\text{Fe}) = 56\ \text{kg/kmol}$. $1000\ \text{kg}$ of ore is loaded.

  1. a) Calculate the mass of iron(III) oxide that actually enters the furnace.
  2. b) Calculate the maximum mass of iron that could be obtained.
  3. c) State what mass of gangue must be removed as waste.
Solve
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An ammonia plant, $\text{N}2 + 3\ \text{H}2 \rightarrow 2\ \text{NH}3$, daily has $28\ \text{t}$ of nitrogen and $8\ \text{t}$ of hydrogen available, and operates with a…

An ammonia plant, $\text{N}_2 + 3\ \text{H}_2 \rightarrow 2\ \text{NH}_3$, daily has $28\ \text{t}$ of nitrogen and $8\ \text{t}$ of hydrogen available, and operates with a yield of $95\ \%$ ($M(\text{N}_2) = 28\ \text{kg/kmol}$; $M(\text{H}_2) = 2\ \text{kg/kmol}$; $M(\text{NH}_3) = 17\ \text{kg/kmol}$).

  1. a) Express both masses in kmol.
  2. b) Determine the limiting reactant.
  3. c) Calculate the theoretical daily production of ammonia, in metric tons.
  4. d) Calculate the actual production with the specified yield.
  5. e) Calculate the metric tons of hydrogen left over each day and explain what should be done with them in the plant.
Solve
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A blast furnace processes $1000\ \text{kg}$ of ore with $80\ \%$ of $\text{Fe}2\text{O}3$ according to…

A blast furnace processes $1000\ \text{kg}$ of ore with $80\ \%$ of $\text{Fe}_2\text{O}_3$ according to $\text{Fe}_2\text{O}_3 + 3\ \text{CO} \rightarrow 2\ \text{Fe} + 3\ \text{CO}_2$, with a yield of $90\ \%$ ($M(\text{Fe}_2\text{O}_3) = 160\ \text{kg/kmol}$; $M(\text{Fe}) = 56\ \text{kg/kmol}$; $M(\text{CO}_2) = 44\ \text{kg/kmol}$).

  1. a) Calculate the mass of iron(III) oxide contained in the feed.
  2. b) Calculate the theoretical mass of iron.
  3. c) Calculate the actual mass of iron with the furnace's yield.
  4. d) Calculate the mass of carbon dioxide generated by the reduction reaction.
  5. e) The process also uses coke (carbon) as a fuel and as a source of $\text{CO}$: explain why total emissions per metric ton of steel are higher than calculated in d) and cite a technological pathway to reduce them.
Solve
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A cement plant loads $1000\ \text{kg}$ of limestone with $90\ \%$ of $\text{CaCO}3$ (the rest being inert impurities) into its kiln. The reaction is…

A cement plant loads $1000\ \text{kg}$ of limestone with $90\ \%$ of $\text{CaCO}_3$ (the rest being inert impurities) into its kiln. The reaction is $\text{CaCO}_3 \rightarrow \text{CaO} + \text{CO}_2$, with $M(\text{CaCO}_3) = 100\ \text{kg/kmol}$, $M(\text{CaO}) = 56\ \text{kg/kmol}$ and $M(\text{CO}_2) = 44\ \text{kg/kmol}$, and the yield of the kiln is $95\ \%$.

  1. a) Calculate the mass of calcium carbonate contained in the feed.
  2. b) Calculate the theoretical mass and actual mass of quicklime obtained.
  3. c) Calculate the mass of carbon dioxide generated by the reaction.
  4. d) Propose two technological measures to reduce the carbon footprint of cement manufacturing and briefly justify each one.
Solve

Chains of reactions and recycling

Sulfuric acid is not made in one step, and an ammonia reactor never converts all of its nitrogen in one trip. How do you count product through several steps, and what happens to the gas that does not react?

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The manufacture of sulfuric acid from sulfur occurs in three stages: $\text{S} + \text{O}2 \rightarrow \text{SO}2$;…

The manufacture of sulfuric acid from sulfur occurs in three stages: $\text{S} + \text{O}_2 \rightarrow \text{SO}_2$; $2\ \text{SO}_2 + \text{O}_2 \rightarrow 2\ \text{SO}_3$; $\text{SO}_3 + \text{H}_2\text{O} \rightarrow \text{H}_2\text{SO}_4$. The sequence of transformations is shown schematically in the figure:

S SO₂ SO₃ H₂SO₄ + O₂ + O₂ + H₂O
  1. a) By following the sulfur atoms through the three equations, deduce how many moles of sulfuric acid are obtained per mole of initial sulfur.
  2. b) With $M(\text{S}) = 32\ \text{kg/kmol}$ and $M(\text{H}_2\text{SO}_4) = 98\ \text{kg/kmol}$, calculate the metric tons of acid produced by a plant from $32\ \text{t}$ of sulfur.
Solve
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Many sulfuric acid plants start from pyrite, an ore of $\text{FeS}2$. The first stage is roasting:…

Many sulfuric acid plants start from pyrite, an ore of $\text{FeS}_2$. The first stage is roasting: $4\ \text{FeS}_2 + 11\ \text{O}_2 \rightarrow 2\ \text{Fe}_2\text{O}_3 + 8\ \text{SO}_2$; then, $\text{SO}_2$ is oxidized to $\text{SO}_3$ and this is hydrated to $\text{H}_2\text{SO}_4$ ($M(\text{FeS}_2) = 120\ \text{kg/kmol}$; $M(\text{H}_2\text{SO}_4) = 98\ \text{kg/kmol}$; $M(\text{Fe}) = 56\ \text{kg/kmol}$). $1000\ \text{kg}$ of ore with $60\ \%$ pyrite content is processed.

  1. a) Calculate the kmol of $\text{FeS}_2$ processed.
  2. b) Using the sulfur atoms, verify that each mole of $\text{FeS}_2$ leads to $2\ \text{mol}$ of $\text{H}_2\text{SO}_4$, and calculate the mass of acid obtained.
  3. c) The iron(III) oxide generated during roasting can be sent to a blast furnace: calculate the mass of recoverable iron and comment on the economic and environmental advantage of integrating two processes in this way.
Solve
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In a Haber plant operating at high pressure and about $450\ \celsius$, only $15\ \%$ of the nitrogen reacts on each pass through the reactor. $100\ \text{kmol}$ of…

In a Haber plant operating at high pressure and about $450\ \celsius$, only $15\ \%$ of the nitrogen reacts on each pass through the reactor. $100\ \text{kmol}$ of $\text{N}_2$ enters with sufficient hydrogen ($M(\text{NH}_3) = 17\ \text{kg/kmol}$).

  1. a) Calculate the kmol of ammonia obtained in one pass and its mass.
  2. b) The unreacted gas is recirculated to the reactor: explain why, as a result, the overall nitrogen utilization approaches $100\ \%$ even though the conversion per pass is low.
  3. c) Relate recirculation to the economic and environmental efficiency of the process (raw material and energy per metric ton of product).
  4. d) The process is exothermic but requires compressing the gases and maintaining the temperature: comment on what these conditions mean for the plant's energy consumption and why industry seeks more effective catalysts.
Solve

Atom economy and environmental impact of industrial processes

Two bars compare, for each route to obtain copper, which part of the mass of the reactants ends up as the desired copper and which as by-product: in route A (CuO + H₂) almost all of it is copper, and in route B (Fe + CuSO₄) most of it is FeSO₄ waste. Route A: CuO + H₂ → Cu + H₂O mass of reactants Cu H₂O higher atom economy Route B: Fe + CuSO₄ → Cu + FeSO₄ mass of reactants Cu FeSO₄ lower atom economy desired product by-product
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Copper can be obtained via two routes: A) $\text{CuO} + \text{H}2 \rightarrow \text{Cu} + \text{H}2\text{O}$; B)…

Copper can be obtained via two routes: A) $\text{CuO} + \text{H}_2 \rightarrow \text{Cu} + \text{H}_2\text{O}$; B) $\text{Fe} + \text{CuSO}_4 \rightarrow \text{Cu} + \text{FeSO}_4$ ($M(\text{CuO}) = 80\ \text{g/mol}$; $M(\text{H}_2) = 2\ \text{g/mol}$; $M(\text{CuSO}_4) = 160\ \text{g/mol}$; $M(\text{Fe}) = 56\ \text{g/mol}$; $M(\text{Cu}) = 64\ \text{g/mol}$). The atom economy of a route is the percentage represented by the mass of the desired product over the total mass of the reactants.

  1. a) Calculate the atom economy of each route.
  2. b) Decide which is "greener" according to that criterion and justify your answer.
  3. c) State two additional factors (economic, energetic or environmental) that a company would consider before choosing a route and comment on why the less atom-efficient route might end up being used.
Solve
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The hydrogen consumed by the Haber process is mostly obtained from methane; the overall process can be written as…

The hydrogen consumed by the Haber process is mostly obtained from methane; the overall process can be written as $\text{CH}_4 + 2\ \text{H}_2\text{O} \rightarrow \text{CO}_2 + 4\ \text{H}_2$ ($M(\text{CO}_2) = 44\ \text{g/mol}$; $M(\text{NH}_3) = 17\ \text{g/mol}$). In the synthesis, $\text{N}_2 + 3\ \text{H}_2 \rightarrow 2\ \text{NH}_3$.

  1. a) Calculate the moles of hydrogen required for each mole of ammonia.
  2. b) Calculate the moles of carbon dioxide emitted in obtaining that hydrogen per mole of ammonia.
  3. c) Calculate the kilograms of $\text{CO}_2$ emitted per kilogram of ammonia manufactured using this "gray hydrogen".
  4. d) With green hydrogen (water electrolysis using renewable electricity), state what that direct emission would be and comment on what other indirect emissions might still exist in ammonia manufacturing.
Solve
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The calcination of limestone in cement manufacturing is $\text{CaCO}3 \rightarrow \text{CaO} + \text{CO}2$, with $M(\text{CaCO}3) = 100\ \text{kg/kmol}$ and…

The calcination of limestone in cement manufacturing is $\text{CaCO}_3 \rightarrow \text{CaO} + \text{CO}_2$, with $M(\text{CaCO}_3) = 100\ \text{kg/kmol}$ and $M(\text{CO}_2) = 44\ \text{kg/kmol}$. A cement plant calcines $1000\ \text{kg}$ of pure limestone per day.

  1. a) Calculate the mass of carbon dioxide generated each day by the chemical reaction itself.
  2. b) Calculate the tons emitted per year if the plant operates for $300$ days.
  3. c) The kiln is heated by burning fuel: explain why the plant's actual carbon footprint exceeds the calculated value and why cement is listed among the highest-emitting materials.
Solve

Back to the start: the missing grams in the kiln did not vanish. Some of the calcium carbonate never decomposed, some product was lost in handling, and side reactions or equilibrium kept the percent yield below 100%. Atoms are conserved; it is the useful product that comes up short.

Summary

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