4.4: Determining The Limiting Reactant - Chemistry LibreTexts

Limiting Reactants in Solutions

The concept of limiting reactants applies to reactions carried out in solution as well as to reactions involving pure substances. If all the reactants but one are present in excess, then the amount of the limiting reactant may be calculated as illustrated in Example \(\PageIndex{2}\).

Example

Because the consumption of alcoholic beverages adversely affects the performance of tasks that require skill and judgment, in most countries it is illegal to drive while under the influence of alcohol. In almost all US states, a blood alcohol level of 0.08% by volume is considered legally drunk. Higher levels cause acute intoxication (0.20%), unconsciousness (about 0.30%), and even death (about 0.50%). The Breathalyzer is a portable device that measures the ethanol concentration in a person’s breath, which is directly proportional to the blood alcohol level. The reaction used in the Breathalyzer is the oxidation of ethanol by the dichromate ion:

\[ 3CH_3 CH_2 OH(aq) + \underset{yellow-orange}{2Cr_2 O_7^{2 -}}(aq) + 16H ^+ (aq) \underset{H_2 SO_4 (aq)}{\xrightarrow{\hspace{10px} Ag ^+\hspace{10px}} } 3CH_3 CO_2 H(aq) + \underset{green}{4Cr^{3+}} (aq) + 11H_2 O(l) \]

When a measured volume (52.5 mL) of a suspect’s breath is bubbled through a solution of excess potassium dichromate in dilute sulfuric acid, the ethanol is rapidly absorbed and oxidized to acetic acid by the dichromate ions. In the process, the chromium atoms in some of the Cr2O72− ions are reduced from Cr6+ to Cr3+. In the presence of Ag+ ions that act as a catalyst, the reaction is complete in less than a minute. Because the Cr2O72− ion (the reactant) is yellow-orange and the Cr3+ ion (the product) forms a green solution, the amount of ethanol in the person’s breath (the limiting reactant) can be determined quite accurately by comparing the color of the final solution with the colors of standard solutions prepared with known amounts of ethanol.

A Breathalyzer reaction with a test tube before (a) and after (b) ethanol is added. When a measured volume of a suspect’s breath is bubbled through the solution, the ethanol is oxidized to acetic acid, and the solution changes color from yellow-orange to green. The intensity of the green color indicates the amount of ethanol in the sample.

A typical Breathalyzer ampul contains 3.0 mL of a 0.25 mg/mL solution of K2Cr2O7 in 50% H2SO4 as well as a fixed concentration of AgNO3 (typically 0.25 mg/mL is used for this purpose). How many grams of ethanol must be present in 52.5 mL of a person’s breath to convert all the Cr6+ to Cr3+?

Given: volume and concentration of one reactant

Asked for: mass of other reactant needed for complete reaction

Strategy:

1. Calculate the number of moles of Cr2O72− ion in 1 mL of the Breathalyzer solution by dividing the mass of K2Cr2O7 by its molar mass.
2. Find the total number of moles of Cr2O72− ion in the Breathalyzer ampul by multiplying the number of moles contained in 1 mL by the total volume of the Breathalyzer solution (3.0 mL).
3. Use the mole ratios from the balanced chemical equation to calculate the number of moles of C2H5OH needed to react completely with the number of moles of Cr2O72− ions present. Then find the mass of C2H5OH needed by multiplying the number of moles of C2H5OH by its molar mass.

Solution:

A In any stoichiometry problem, the first step is always to calculate the number of moles of each reactant present. In this case, we are given the mass of K2Cr2O7 in 1 mL of solution, which can be used to calculate the number of moles of K2Cr2O7 contained in 1 mL:

\( \dfrac{moles\: K_2 Cr_2 O_7} {1\: mL} = \dfrac{(0 .25\: \cancel{mg}\: K_2 Cr_2 O_7 )} {mL} \left( \dfrac{1\: \cancel{g}} {1000\: \cancel{mg}} \right) \left( \dfrac{1\: mol} {294 .18\: \cancel{g}\: K_2 Cr_2 O_7} \right) = 8.5 \times 10 ^{-7}\: moles \)

B Because 1 mol of K2Cr2O7 produces 1 mol of Cr2O72− when it dissolves, each milliliter of solution contains 8.5 × 10−7 mol of Cr2O72−. The total number of moles of Cr2O72− in a 3.0 mL Breathalyzer ampul is thus

\( moles\: Cr_2 O_7^{2-} = \left( \dfrac{8 .5 \times 10^{-7}\: mol} {1\: \cancel{mL}} \right) ( 3 .0\: \cancel{mL} ) = 2 .6 \times 10^{-6}\: mol\: Cr_2 O_7^{2–} \)

C The balanced chemical equation tells us that 3 mol of C2H5OH is needed to consume 2 mol of Cr2O72− ion, so the total number of moles of C2H5OH required for complete reaction is

\( moles\: of\: C_2 H_5 OH = ( 2.6 \times 10 ^{-6}\: \cancel{mol\: Cr_2 O_7 ^{2-}} ) \left( \dfrac{3\: mol\: C_2 H_5 OH} {2\: \cancel{mol\: Cr _2 O _7 ^{2 -}}} \right) = 3 .9 \times 10 ^{-6}\: mol\: C _2 H _5 OH \)

As indicated in the strategy, this number can be converted to the mass of C2H5OH using its molar mass:

\( mass\: C _2 H _5 OH = ( 3 .9 \times 10 ^{-6}\: \cancel{mol\: C _2 H _5 OH} ) \left( \dfrac{46 .07\: g} {\cancel{mol\: C _2 H _5 OH}} \right) = 1 .8 \times 10 ^{-4}\: g\: C _2 H _5 OH \)

Thus 1.8 × 10−4 g or 0.18 mg of C2H5OH must be present. Experimentally, it is found that this value corresponds to a blood alcohol level of 0.7%, which is usually fatal.

Exercise \(\PageIndex{2}\)

The compound para-nitrophenol (molar mass = 139 g/mol) reacts with sodium hydroxide in aqueous solution to generate a yellow anion via the reaction

Because the amount of para-nitrophenol is easily estimated from the intensity of the yellow color that results when excess NaOH is added, reactions that produce para-nitrophenol are commonly used to measure the activity of enzymes, the catalysts in biological systems. What volume of 0.105 M NaOH must be added to 50.0 mL of a solution containing 7.20 × 10−4 g of para-nitrophenol to ensure that formation of the yellow anion is complete?

Answer: 4.93 × 10−5 L or 49.3 μL

In Examples 4.4.1 and 4.4.2, the identities of the limiting reactants are apparent: [Au(CN)2]−, LaCl3, ethanol, and para-nitrophenol. When the limiting reactant is not apparent, it can be determined by comparing the molar amounts of the reactants with their coefficients in the balanced chemical equation. The only difference is that the volumes and concentrations of solutions of reactants, rather than the masses of reactants, are used to calculate the number of moles of reactants, as illustrated in Example \(\PageIndex{3}\).

Example \(\PageIndex{3}\)

When aqueous solutions of silver nitrate and potassium dichromate are mixed, an exchange reaction occurs, and silver dichromate is obtained as a red solid. The overall chemical equation for the reaction is as follows:

\(2AgNO_3(aq) + K_2Cr_2O_7(aq) \rightarrow Ag_2Cr_2O_7(s) + 2KNO_3(aq) \)

What mass of Ag2Cr2O7 is formed when 500 mL of 0.17 M K2Cr2O7 are mixed with 250 mL of 0.57 M AgNO3?

Given: balanced chemical equation and volume and concentration of each reactant

Asked for: mass of product

Strategy:

1. Calculate the number of moles of each reactant by multiplying the volume of each solution by its molarity.
2. Determine which reactant is limiting by dividing the number of moles of each reactant by its stoichiometric coefficient in the balanced chemical equation.
3. Use mole ratios to calculate the number of moles of product that can be formed from the limiting reactant. Multiply the number of moles of the product by its molar mass to obtain the corresponding mass of product.

Solution:

A The balanced chemical equation tells us that 2 mol of AgNO3(aq) reacts with 1 mol of K2Cr2O7(aq) to form 1 mol of Ag2Cr2O7(s) (Figure \(\PageIndex{2}\)). The first step is to calculate the number of moles of each reactant in the specified volumes:

\[ moles\: K_2 Cr_2 O_7 = 500\: \cancel{mL} \left( \dfrac{1\: \cancel{L}} {1000\: \cancel{mL}} \right) \left( \dfrac{0 .17\: mol\: K_2 Cr_2 O_7} {1\: \cancel{L}} \right) = 0 .085\: mol\: K_2 Cr_2 O_7 \]

\[ moles\: AgNO_3 = 250\: \cancel{mL} \left( \dfrac{1\: \cancel{L}} {1000\: \cancel{mL}} \right) \left( \dfrac{0 .57\: mol\: AgNO_3} {1\: \cancel{L}} \right) = 0 .14\: mol\: AgNO_3 \]

B Now determine which reactant is limiting by dividing the number of moles of each reactant by its stoichiometric coefficient:

\[K_2 Cr_2 O_7: \: \dfrac{0 .085\: mol} {1\: mol} = 0 .085 \]

\[ AgNO_3: \: \dfrac{0 .14\: mol} {2\: mol} = 0 .070 \]

Because 0.070 < 0.085, we know that AgNO3 is the limiting reactant.

C Each mole of Ag2Cr2O7 formed requires 2 mol of the limiting reactant (AgNO3), so we can obtain only 0.14/2 = 0.070 mol of Ag2Cr2O7. Finally, convert the number of moles of Ag2Cr2O7 to the corresponding mass:

\[ mass\: of\: Ag_2 Cr_2 O_7 = 0 .070\: \cancel{mol} \left( \dfrac{431 .72\: g} {1 \: \cancel{mol}} \right) = 30\: g \: Ag_2 Cr_2 O_7 \]

The Ag+ and Cr2O72− ions form a red precipitate of solid Ag2Cr2O7, while the K+ and NO3− ions remain in solution. (Water molecules are omitted from molecular views of the solutions for clarity.)

Exercise \(\PageIndex{3}\)

Aqueous solutions of sodium bicarbonate and sulfuric acid react to produce carbon dioxide according to the following equation:

\(2NaHCO_3(aq) + H_2SO_4(aq) \rightarrow 2CO_2(g) + Na_2SO_4(aq) + 2H_2O(l)\)

If 13.0 mL of 3.0 M H2SO4 are added to 732 mL of 0.112 M NaHCO3, what mass of CO2 is produced?

Answer: 3.4 g

Limiting Reactant Problems Using Molarities: https://youtu.be/eOXTliL-gNw