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Assignment 80 THE LIMITING REAGENT, AND THE % YIELD FOR A REACTION

This assignment extends a previous one where a given chemical equation was used as a means of calculating the theoretical yield for the reaction. In that assignment, it was assumed (or stated) that all other reactants in the equation were present in sufficient quantities to allow complete reaction of the given reactant. In the laboratory, however, the amount of each reactant involved must be considered. Since the mole proportions involved in the reaction are fixed by the equation, the extent of a reaction is limited by the amount of the reactant present which produces the least amount of the desired product. This limit can be determined by multiplying the moles of each reactant present by the appropriate conversion factor.

For illustrations of the method of calculation, the following chemical equation will be used: 5 SO2 (g) + 2 MnO4 + 2 H2O
6

( which indicates: 5 mol + 2 mol + 2 mol yields 5 mol

From this balanced equation and the amounts of the reactants given for use, the theoretical amount of the products can be determined, assuming that the reaction continues to occur until one of the reactants is totally consumed.

Examples: 1.

(See reaction above.)

What is the maximum quantity of Mn2+(in moles) which can be formed from a mixture of 20.0 liters (STP) of SO2 and 0.300 moles of MnO4! in excess water? Start by determining the moles of Mn which would be produced (theoretically) from each of the above quantities of reactant, so as to determine which reactant is the limiting reagent. 2 mol Mn 2+ . For SO2 , the appropriate conversion factor is 5 mol SO 2
2+

Therefore, the moles Mn which can be produced from 20.0 LSTP of SO2 is: 1 mol SO2 2 mol Mn 2+ = 0.357 mol Mn 2 + x 20.0 LSTP SO 2 x 22.4 LSTP 5 mol SO 2 2 mol Mn 2 + For MnO4, the appropriate conversion factor is 2 mol MnO 4
2+

2+

Thus, the moles Mn which can be produced from 0.300 moles of MnO4 is: 2 mol Mn 2 + = 0.300 mol Mn 2 + 0.300 mol MnO x 4 2 mol MnO 4
2+ Under these conditions, the amount of Mn that can be formed is limited to 0.300 mol Mn2+ by the amount of MnO4 reactant present. No matter how much SO2 gas is present over the amount required to produce 0.300 mol 2+ 2+ Mn , no more than 0.300 mol Mn can possibly be produced when starting with 0.300 mol of MnO4 ion. Some of the SO2 will remain unreacted (excess SO2).

So, the MnO4 reactant is the limiting reagent for this reaction. In the present example, when 0.300 mol Mn are formed, the number of liters(STP) of SO2 used in the reaction is: 5 mol SO 2 22.4 LSTP SO 2 = 16.8 LSTP SO 2 used 0.300 mol Mn 2 + x x 2+ 2 mol Mn 1 mol SO 2
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2+

(20.0 LSTP SO2 originally) - (16.8 LSTP SO2 used ) =

In summary for the example above,

3.2 LSTP SO2 remaining

the limiting reagent is MnO4 (since the MnO4 reagent will become exhausted during reaction, with none remaining); the theoretical yield of Mn is 0.300 mol Mn (since that is the maximum amount that can be produced from the original MnO4); the theoretical amount remaining of the other reactant, SO2 gas, is 3.2 LSTP leftover unreacted.
2+ 2+

2.

How many grams of SO42 are formed if 0.80 grams of SO2 (MW = 64 g/mol) are bubbled into 30.0 mL of 0.10 M MnO4 in acidic solution?

To determine the limiting reagent, calculate the grams of SO4 that can be formed from each given reactant. The 2 2 MW of SO4 is 96 g/mol SO4 .
2

From SO2 gas , 1 mol SO2 0.80 g SO 2 x 64 g SO2

5 mol SO 2 4 x 5 mol SO 2

96 g SO 2 4 x 1 mol SO2 4

= 1.20 g SO 2 4 = 0.72 g SO 2 4

2

5 mol SO 2 4 x 2 mol MnO 4

96 g SO 2 4 x 1 mol SO2 4

Thus, the amount of SO4 produced is limited to 0.72 grams (the lesser amount), and the limiting reagent is the MnO4 solution. The SO2 reagent is present in excess. In example 2 it is also possible to determine the limiting reagent by calculating mol SO4 rather than grams SO4 , then 2 2 the limited number of moles of SO4 may be converted to grams of SO4 in a separate step. The essential feature is the solving for the same dimensional units starting with each given reactant, whether the units solved for are grams 2 2 SO4 , or moles SO4 , or some other quantity of interest in the problem.
2 2

3.

What would be the final composition of a mixture, in liters(STP) of each compound, when 10.0 liters(STP) of SO2 and 10.0 liters(STP) of O2 react to completion as follows: 2 SO2 (g) + O2 (g) 2 SO3 (g)

2 mol + 1 mol yields 2 mol )

First, determine the limiting reagent, by determining the limited amount of product formed. From SO2 : 1 mol SO 2 LSTP SO3 = 10.0 LSTP x 22.4 LSTP SO 2 From O2 : 1 mol SO2 LSTP SO3 = 10.0 LSTP x 22.4 LSTP SO2 2 mol SO3 x 2 mol SO 2 2 mol SO3 x 1 mol SO 2 22.4 LSTP SO3 x 1 mol SO3 22.4 LSTP SO3 x 1 mol SO3 = 10.0 LSTP SO3 = 20.0 LSTP SO3
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Thus, the theoretical yield of SO3 product is limited to 10.0 LSTP; the limiting reagent is SO2. (Note how readily the numbers and dimensions cancel in this form of writing the problem.) Finally, calculate the amount of any reagent left over. Since the reaction was limited by the amount of SO2 present, all of the SO2 will be used up in the reaction; however, some O2 will remain. The amount of O2 which reacted can be determined (by use of appropriate conversion factors) from the amount of SO2 which reacts. 1 mol SO 2 LSTP O2 reacted = 10.0 LSTP SO 2 x 22.4 LSTP SO 2 1 mol O 2 x 2 mol SO 2 22.4 LSTP O 2 x 1 mol O2 = 5.00 LSTP O 2 reacted

LSTP O2 remaining = ( 10.0 LSTP O2 originally ) ( 5.00 LSTP O2 reacted ) = 5.0 LSTP O2 in excess
It is equally acceptable to determine the liters of O2 reacted by calculating from the quantity of SO3 formed, 10.0 liters SO3. 1 mol SO3 LSTP O2 reacted = 10.0 LSTP SO3 x 22.4 LSTP SO3 In summary for example 3: SO2 O2 SO3 Original liters(STP) 10.0 10.0 0.0 Final liters(STP) 0.0 5.0 10.0 1 mol O 2 x 2 mol SO3 22.4 LSTP O2 x 1 mol O2 = 5.00 LSTP O 2 reacted

An additional facet of calculations from chemical equations is related to the laboratory realities of carrying out the reaction. The actual yield of products, as obtained from a reaction in the laboratory, is seldom as large as the theoretical yield calculated from the chemical equation for the reaction. There may be several reasons for such a discrepancy: 1) Experimental technique loss of part of the product due to poor technique on the part of the laboratory worker or to the difficulties in separating the product from the reactants (i.e., if the reaction is carried out in a solvent, some of the product remains dissolved in the solvent to give a saturated solution). 2) Incompleteness of reaction all reactions do not bring about the complete conversion of the reactants to products; most reactions are reversible and proceed only until chemical equilibrium is reached. 3) Side reactions although the equation used in making the calculations may describe the principal reaction which is occurring in a system, several other reactions may be occurring simultaneously and these will use up the reactants to form different products (often called by-products).

It is desirable to obtain as much of the product as possible from any reaction. The measure of the effectiveness of the procedure is the percentage yield. As in the case of any other percentage, this is the fraction of the total possible yield multiplied by 100: % yield = actual yield x 100 theoretical yield

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Examples: Given this equation: Mg3N2 + 6 H2O 3 Mg(OH)2 + 2 NH3

( which indicates:

1 mol + 6 mol

yields

3 mol

2 mol )

Under actual laboratory conditions, it is usually difficult to obtain 2 mol of NH3 for every 1 mol of Mg3N2 used. From the equation and from the original amount of Mg3N2 , the theoretical yield can be calculated assuming complete (100%) reaction as written. Then, a comparison of the actual yield of NH3 with the theoretical yield gives the % yield.

1.

If 3.0 moles of NH3 are obtained from a reaction of 2.0 moles of Mg3N2 with excess H2O , what is the percentage yield of NH3 ?

The actual yield is given information, 3.0 mol NH3 ; it is data resulting only from a laboratory experiment. The theoretical yield is calculated (in the same dimensions, mol NH3) by means of the balanced chemical equation and the given amount of limiting reactant, 2.0 mol Mg3N2: 2 mol NH 3 mol NH3 ( theor .) = 2.0 mol Mg3 N 2 x 1 mol Mg N 3 2 Then the percentage yield is evaluated:
% yield =

= 4.0 mol NH3

actual yield 3.0 mol NH 3 x 100 = x 100 = 75% yield of NH3 theor . yield 4.0 mol NH3

(Note that the actual yield and the theoretical yield may be expressed in any units moles, grams, liters(STP) as long as the same units are used for both the yields. Percentage yield is always dimensionless, since the numerator and denominator must have the same dimensions.)

2.

If 10.0 grams H2O , on reaction with excess Mg3N2 , yields 1.0 liter(STP) NH3 , what is the percentage yield of this reaction?

The actual yield (given) is: 1.0 LSTP NH3 The theoretical yield (calculated in the same units, liters(STP) of NH3) is: 1 mol H 2 O LSTP NH3 ( theor .) = 10.0 g H 2 O x 18.0 g O H2 2 mol NH3 x 6 mol O H2 22.4 LSTP NH3 x 1 mol NH3 = 4.15 LSTP NH3

The percentage yield (calculated from the above) is: actual yield 1.0 LSTP x 100 = % yield = x 100 = 24% yield theor . yield 4.15 LSTP

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3.

From the reaction of 5.0 lbs Mg3N2 and 6.0 lbs H2O, 1.2 lb NH3 is obtained. What is the percentage yield?

Since the mass units are expressed in lb, it is more convenient to express the dimensions of molecular weight as "lb/lb-mol". This molecular weight relationship thereby defines the "lb-mol" dimensional unit, just as the more usual "(gram-)mol" was defined by expressing the dimensions of molecular weight as "grams/(gram-)mol". Therefore, MW of Mg3N2 = 102 lb/lb-mol and MW of H2O = 18.0 lb/lb-mol. The actual yield is given as 1.2 lb NH3. The theoretical yield (in the units, lb NH3) is determined by first calculating for each given reactant, in order to determine which reactant limits the yield. All the conversion factors, which would normally be expressed in mol dimensions, may be expressed in lb-mol dimensions here. From Mg3N2 : 1 lb- mol Mg 2 N3 2 lb- mol NH3 17.0 lb NH3 lb NH 3 = 5.0 lbs Mg3 N 2 x 102 lb Mg N x 1 lb- mol Mg N x 1 lb- mol NH = 1.7 lb NH3 3 2 3 3 2 From H2O : 1 lb- mol H 2 O 2 lb- mol NH3 17.0 lb NH3 = 2.8 lb NH3 lb NH3 = 6.0 lbs H 2 O x 18.0 lb O x 6 lb- mol O x 1 lb- mol NH3 H2 H2 In conclusion: the theoretical yield is 1.7 lb NH3 , limited by the Mg3N2 reactant. The percentage yield then is calculated: actual yield 1.2 lb NH3 x 100 = % yield = x 100 = 71% yield theor . yield 1.7 lb NH3 * * * * * * * * * *

In all of the examples above, the calculation involved a conversion factor based on a completely balanced chemical reaction. However, it is sometimes possible to calculate the theoretical yield or the percentage yield without having a complete chemical equation, as follows: If the reactant and the product both contain a limiting ELEMENT (an element appearing in only one reactant and only one product), the conversion factor may be obtained from a balanced expression based on the element which limits the process, and the theoretical yield is calculated by means of this conversion factor.
Examples: 1. Reactant: NaCl Product: AgCl

Cl is the limiting element (the common element in both reactant and product) and is balanced in this fashion: 1 AgCl 1 mol AgCl Conversion factor: 1 mol NaCl It is assumed that no other reactant or product contains the limiting element, Cl. 1 NaCl

2.

Reactant: Pb3O4

Product: Pb

Pb is the limiting element and is balanced in this fashion: 3 Pb (so that the limiting element, Pb, is balanced) 3 mol Pb Conversion factor: 1 mol Pb3 O 4 1 Pb3O4

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3.

Reactant: Na

Product: Na2S

Na is the limiting element and is balanced in this fashion: 1 Na2S 1 mol Na 2 S Conversion factor: 2 mol Na 2 Na

4.

Reactant: Cr2O3

Product: K2Cr2O7

Both Cr and O are present in both the reactant and the product, but oxygen is prevalent in many reagents (for example, in H2O, or KOH, or peroxides, or oxo-complexes, or O2 of the atmosphere). Thus oxygen probably enters the reaction from other substances besides the two listed, and would NOT be limited to these two compounds. The limiting element is Cr and is balanced in this fashion: 1 K2Cr2O7 1 mol K 2 Cr 2 O7 Conversion factor: 1 mol Cr 2 O3 1 Cr2O3

5.

Reactant: Ni3O4

Product: Ni2O3

Ni is the limiting element and is balanced in this fashion: 3 Ni2O3 3 mol Ni 2 O3 Conversion factor: 2 mol Ni3 O 4 2 Ni3O4

In order to determine the percentage yield, the original amount of reactant and the amount of product actually obtained must be given. The theoretical yield is calculated with a conversion factor deduced as above.
Examples: 1. If 2.0 mol of iron ore, Fe2O3 , gives 3.5 mol of Fe upon reduction, what is the percentage yield?

The actual yield = 3.5 mol Fe (given value) The theoretical yield is calculated by means of the limiting element relationship: (Fe is balanced) 2 mol Fe mol Fe ( theor .) = 2.0 mol Fe2 O3 x 1 mol Fe2 O3 Fe2O3 2 Fe = 4.0 mol Fe

The percentage yield is then calculated: actual yield 3.5 mol Fe % yield = x 100 = x 100 = 88% yield theor . yield 4.0 mol Fe

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2.

If 10.0 grams of Fe are produced from 16.0 grams of Fe2O3 , what is the percentage yield?

The actual yield = 10.0 g Fe (given value) The theoretical yield is calculated with the limiting element relationship: Fe2O3 2 Fe (Fe is balanced) 2 mol Fe x 1 mol Fe2 O3 55.8 g Fe x = 11.2 g Fe 1 mol Fe

1 mol Fe2 O3 mol Fe ( theor .) = 16.0 g Fe2 O3 x 160.0 g Fe2 O3

The percentage yield is then calculated: % yield = 10.0 g Fe actual yield x 100 = 11.2 g Fe theor . yield x 100 = 89.2% yield

In many laboratory procedures, reagents are dissolved in a solvent such as water before the reagents are mixed. Then the quantity of reagents used in the reaction is regulated by measurement of the volume of solution. Again, recall that ( L x mol/L ) = mol of reagent.

Example (using the "limiting element" method): What is the % yield of solid silver acetate, AgOAc, if 30.0 mL of 0.500 M AgNO3 solution and 30.0 mL of 0.400 M Ca(OAc)2 solution are mixed and 0.0120 moles of AgOAc are obtained?

Actual yield = 0.0120 mol AgOAc (given value) Theor. yield is calculated by first determining which reagent limits the reaction. For the AgNO3 reactant, the necessary relationship is based upon the limiting element, silver. 1 AgOAc (Ag is balanced) mol AgNO3 mol AgOAc ( theor .) = 30.0 x 103 L x 0.500 L 1 AgNO3 1 mol AgOAc x 1 mol AgNO 3 = 1.50 x 10 2 mol AgOAc

For the Ca(OAc)2 reactant, the necessary relationship is based upon the limiting ionic group, OAc (acetate ion). 1 Ca(OAc)2 2 AgOAc (OAc is balanced)

mol Ca(OAc ) 2 2 mol AgOAc mol AgOAc ( theor .) = 30.0 x 10 3 L x 0.400 x L 1 mol Ca(OAc ) 2
2

= 2.40 x 10 2 mol AgOAc

The theor. yield, then, is concluded to be 1.50 x 10 mol AgOAc, limited by the AgNO3 reagent. The percentage yield is then calculated: 0.0120 mol AgOAc actual yield % yield = x 100 = 0.0150 mol AgOAc theor . yield x 100 = 80.0% yield

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There is an alternate way to solve this same example, using one's chemical knowledge to interpret the problem in terms of the ions which are reacting. For future reference, the sequence of steps is as follows: The original reagents are Ag NO3 and Ca (OAc)2 , which are soluble ionic compounds. Therefore the original amounts of each ION can be calculated. mol AgNO3 1 mol Ag+ + 2 x mol Ag+ = 30.0 x 103 L x 0.500 1 mol AgNO = 1.50 x 10 mol Ag L 3
+ 2+

mol NO3 = 1.50 x 102 mol NO3 (by similar reasoning)

mol Ca(OAc ) 2 mol Ca 2 + = 30.0 x 103 L x 0.400 L mol Ca(OAc )2 mol OAc = 30.0 x 103 L x 0.400 L

+

= 1.20 x 10 2 mol Ca 2 + = 2.40 x 10 2 mol OAc

The reaction then is simply the precipitation of the Ag and OAc ions to form solid AgOAc corresponding to this very easily balanced equation: Ag + OAc
+

AgOAc (s)
2+

(The other ions, NO3 and Ca , are merely spectators and do not participate in the reaction.)

Actual yield = 0.0120 mol AgOAc (given value) Theor. yield requires consideration of the limiting reagent. By inspecting the reaction equation (the ions react + one-to-one) and by comparing the original moles of each reactant (there are fewer moles of the Ag reactant), + we determine that the limiting reagent will be Ag (used up first).
mol OAc leftover = 2.40 x 102 mol orig . 1.50 x 102 mol reacting = 0.90 x 10 mol OAc = 9.0 x 10 mol OAc remaining unreacted . mol AgOAc formed = 1.50 x 102 mol AgOAc ( theoretical yield) The percentage yield is then calculated as before: 0.0120 mol actual yield % yield = x 100 = 80.0% x 100 = 0.0150 mol theor . yield
2 3

) (

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