exp08.

qxd 11/15/13 10:29 AM Page 123

Scimat/Science Source Experiment 8

Limiting Reactant
Calcium oxalate crystals contribute to the formation of kidney stones.

• To determine the limiting reactant in a mixture of two soluble salts Objectives

• To determine the percent composition of each substance in a salt mixture

The following techniques are used in the Experimental Procedure: Techniques

Percent composition: the mass ratio of
a component of a mixture or
compound to the total mass of the
sample times 100

Two factors affect the yield of products in a chemical reaction: (1) the amounts Introduction
(moles) of starting materials (reactants) and (2) the percent yield of the reaction. Percent yield:
Many experimental conditions, for example, temperature and pressure, can be adjusted
冢theoretical yield冣
actual yield
to increase the yield of a desired product in a chemical reaction, but because chemicals 100
react according to fixed mole ratios (stoichiometrically), only a limited amount of
product can form from measured amounts of starting materials. The reactant determin-
ing the amount of product generated in a chemical reaction is called the limiting reac-
Stoichiometrically: by a study of a
tant in the chemical system. chemical reaction using a balanced
To better understand the concept of the limiting reactant, let us look at the reac- equation
tion under investigation in this experiment, the reaction of calcium chloride dihy-
drate, CaCl2•2H2O, and potassium oxalate monohydrate, K2C2O4•H2O, in an aqueous
solution.
CaCl2 • 2H2O(aq) + K2C2O4 • H2O(aq) —›
CaC2O4 •H2O(s) + 2 KCl(aq) + 2 H2O(l) (8.1)
Calcium oxalate monohydrate, CaC2O4•H2O, the product, is an insoluble com-
pound, but is found naturally in a number of diverse locations. It is found in plants,
such as rhubarb leaves, agave, and (in small amounts) spinach, and is the cause of most
kidney stones. In small doses, it causes a severe reaction to the lining of the digestive
tract. However, the handling of calcium oxalate in the laboratory is safe, so long as it is
not transferred to the mouth.
For the reaction system in this experiment, both the calcium chloride and potas-
sium oxalate are soluble salts, but the calcium oxalate is insoluble. The ionic equation Ionic equation: A chemical equation
for the reaction is that presents ionic compounds in the
form in which they exist in aqueous
Ca2+(aq) + 2 Cl–(aq) + 2 K+(aq) + C2O4 2–(aq) + 3 H2O(l) —› solution. See Experiment 6.
CaC2O4 • H2O(s) + 2 Cl–(aq) + 2 K+(aq) + 2 H2O(l) (8.2)

Experiment 8 123
exp08.qxd 11/15/13 10:29 AM Page 124

Spectator ions: cations or anions that
do not participate in any observable
or detectable chemical reaction
Net ionic equation: an equation that
includes only those ions that
participate in the observed chemical
reaction, also presented in
Experiment 6.
Presenting only the ions that show evidence of a chemical reaction (i.e., the forma-
tion of a precipitate) and by removing the spectator ions (i.e., no change of ionic form
during the reaction), we have the net ionic equation for the observed reaction:
Ca2+(aq) + C2O4 2–(aq) + H2O(l) —› CaC2O4 • H2O(s) (8.3)
Calcium oxalate monohydrate is thermally stable below ~90°C but forms the
anhydrous salt, CaC2O4, at temperatures above 110°C.
Therefore, one mole of Ca2+ (from one mole of CaCl2•2H2O, molar mass = 147.02
g/mol) reacts with one mole of C2O42– (from one mole of K2C2O4•H2O, molar mass =
184.24 g/mol) to produce one mole of CaC2O4•H2O (molar mass = 146.12 g/mol). If
the calcium oxalate is heated to temperatures greater than 110°C for drying, then anhy-
drous CaC2O4 (molar mass = 128.10 g/mol) is the product.
In Part A of this experiment the solid reactant salts CaCl2•2H2O and K2C2O4•H2O
form a heterogeneous mixture of unknown composition. The mass of the solid mixture
is measured and then added to water—insoluble CaC2O4•H2O forms. The CaC2O4•H2O
precipitate is collected via gravity filtration and dried, and its mass is measured.
The percent composition of the salt mixture is determined by first testing for
the limiting reactant. In Part B, the limiting reactant for the formation of solid cal-
cium oxalate monohydrate is determined from two precipitation tests of the final
reaction mixture from Part A: (1) the mixture is tested for an excess of calcium ion
with an oxalate reagent—observed formation of a precipitate indicates the presence
of an excess of calcium ion (and a limited amount of oxalate ion) in the salt mix-
ture; (2) the mixture is also tested for an excess of oxalate ion with a calcium
reagent—observed formation of a precipitate indicates the presence of an excess of
oxalate ion (and a limited amount of calcium ion) in the salt mixture.

Calculations The calculations for the analysis of the salt mixture require some attention. “How do I
proceed to determine the percent composition of a salt mixture of CaCl2•2H2O and
K2C2O4•H2O by measuring only the mass of the CaC2O4•H2O precipitate?”
Example: A 0.538-g sample of the salt mixture is added to water and after drying
(to less than 90°C) 0.194 g of CaC2O4•H2O is measured. Tests reveal that
K2C2O4•H2O is the limiting reactant. What is the percent composition of the salt
mixture? Since K2C2O4•H2O is the limiting reactant, how many grams of the
excess CaCl2•2H2O were in the salt mixture?
Solution: Since K2C2O4•H2O is the limiting reactant, then, according to equation
8.1, the moles of K2C2O4•H2O in the salt mixture equals the moles of CaC2O4•H2O
formed. Therefore, the calculated mass of K2C2O4•H2O in the original salt mixture is
1 mol CaC2O4 • H2O
grams K2C2O4 • H2O = 0.194 g CaC2O4 • H2O
146.12 g CaC2O4 • H2O
1 mol K2C2O4 • H2O 184.24 K2C2O4 • H2O
1 mol CaC2O4 • H2O 1 mol K2C2O4 • H2O
Data Analysis, A
= 0.245 g K2C2O4 • H2O in the salt mixture.
The percent by mass of K2C2O4•H2O in the original salt mixture is
0.245 g K2C2O4 • H2O
% K2C2O4 • H2O = 100 = 45.5% K2C2O4 • H2O
0.538 g sample
The mass of the CaCl2•2H2O in the salt mixture is the difference between the mass
of the sample and the mass of K2C2O4•H2O or (0.538 g – 0.245 g =) 0.293 g. The
percent by mass of CaCl2•2H2O in the original salt mixture is
0.538 g – 0.245 g
% CaCl2 • 2H2O = 100 = 54.5% CaCl2 • 2H2O
0.538 g sample

124 Limiting Reactant

exp08.qxd 11/15/13 10:29 AM Page 125

According to equation 8.1, the moles of CaCl2•2H2O that react equals the moles of
K2C2O4•H2O (the limiting reactant) that react equals the moles of CaC2O4•H2O that
precipitate. Therefore, the mass of CaCl2•2H2O (the excess reactant) that reacts is
1 mol CaC2O4• H2O
mass CaCl2 • 2H2O = 0.194 g CaC2O4• H2O
146.12 g CaC2O4 • H2O
1 mol CaCl2 • 2H2O 147.02 g CaCl2 • 2H2O
1 mol CaC2O4 • H2O 1 mol CaCl2 • 2H2O
= 0.195 g CaCl2 • 2H2O reacted

Since 0.293 g CaCl2•2H2O were calculated present in the original salt mixture, then
the mass of excess CaCl2•2H2O is (0.293 g – 0.195 g =) 0.098 g xs CaCl2•2H2O.

Procedure Overview: In Part A, a measured mass of a solid CaCl2•2H2O/K2C2O4•H2O Experimental

salt mixture of unknown percent composition is added to water. The precipitate that Procedure
forms is digested, filtered, and dried, and its mass is measured. Observations from tests
on the supernatant solution in Part B determine which salt in the mixture is the limit- Supernatant: the clear solution that
exists after the precipitate has settled
ing reactant. An analysis of the data provides the determination of the percent compo-
sition of the salt mixture.
Two trials are recommended for this experiment. To hasten the analyses, measure
the mass of duplicate unknown solid salt mixtures in clean 150- or 250-mL beakers
and simultaneously follow the procedure for each. Label the beakers accordingly for
Trial 1 and Trial 2 to avoid the intermixing of samples and solutions.
Obtain about 2–3 g of an unknown CaCl2•2H2O/K2C2O4•H2O salt mixture.
Be aware of the number of significant figures when recording data.

1. Prepare the salt mixture. A. Precipitation of

a. Mass of salt mixture. Measure the mass (±0.001 g) of beaker 1 and record on CaC 2 O 4 •H 2 O from
the Report Sheet for Trial 1. Transfer ~1 g of the salt mixture to the beaker, the Salt Mixture
measure, and record the combined mass. Repeat for Trial 2, beaker 2.
b. Adjust pH of deionized water. Fill a 400-mL beaker with deionized water. Test
with pH paper. If the water is acidic, adjust it to be just basic with drops of 6 M
NH3. If already basic to pH paper, then no addition of NH3 is necessary.1
Data Analysis, A
c. Mix deionized water and salt. Add ~150 mL of the deionized water from Part
A.1b to the salt mixture in beaker 1. Stir the mixture with a stirring rod for 2–3
minutes and then allow the precipitate to settle. Leave the stirring rod in the
beaker. Repeat for Trial 2.
2. Digest the precipitate.2
a. Heat. Cover the beaker with a watch glass and warm the solution on a hot plate
(Figure 8.1, page 126) to a temperature not to exceed 75°C for ~15 minutes.
Periodically stir the solution and, in the meantime, proceed to Part A.3.
b. Cool. After ~15 minutes, remove the heat and allow the precipitate to settle; the
solution does not need to cool to room temperature.

1
Calcium oxalate does not precipitate in an acidic solution because of the formation of H2C2O4 –, an
ion that does not precipitate with Ca2+.
2
Digesting a precipitate in warm water promotes the dissolving of the smaller precipitate particles fol-
lowed by their re-precipitating onto the existing larger particles. The result is a more efficient
filtering process.

Experiment 8 125
exp08.qxd 11/15/13 10:29 AM Page 126

Stirring rod
Watchglass

Water level

Jo A. Beran/Trey Hernandez
Ca C2 O4 precipitate

Gentle heat

Figure 8.1 Warming and digesting the precipitate

c. Wash water. While the precipitate is settling, heat (70–80°C) ~30 mL of deion-
ized water for use as wash water in Part A.5.
3. Set up a gravity (or vacuum3) filtering apparatus. Place your initials (in pencil)
and “Trial 1” on a piece of Whatman No. 42 or Fisherbrand Q2 filter paper,4 fold, and
tear off its corner. Measure and record its mass (±0.001 g). Seal the filter paper into
the filter funnel with a small amount of deionized water. Discard the deionized water
from the receiving flask. Have your instructor inspect your apparatus before continu-
ing. Return to Part A.2b.
4. Withdraw and save supernatant. Once the precipitate has settled and the
supernatant has cleared in Part A.2b, use a dropping pipet to withdraw enough
supernatant to half-fill two 75-mm test tubes labeled “1” and “2.” Save for
Part B.
5. Filter the CaC2O4•H2O precipitate. While the remaining solution of the salt mix-
ture from Part A.4 is still warm, quantitatively transfer the precipitate to the filter
(Figure 8.2). Transfer any precipitate on the wall of the beaker to the filter with the
Rubber policeman: a spatula-like
aid of a rubber policeman; wash any remaining precipitate onto the filter with
rubber tip attached to a stirring rod three or four 5-mL volumes of warm water (from Part A.2c).
6. Dry and measure the amount of CaC2O4•H2O precipitate. Remove the filter
paper and precipitate from the filter funnel. Air-dry the precipitate on the filter paper
until the next laboratory period or dry in a <110°C constant temperature drying
oven for at least 1 hour or overnight. Determine the combined mass (±0.001 g) of
the precipitate and filter paper. Record. Repeat for Trial 2.
7. Formula of the precipitate. If the precipitate is air-dried, the precipitate is
CaC2O4•H2O; if oven-dried at ≥110°C, the precipitate is the anhydrous CaC2O4.
Enter the mass of the dried precipitate on the Report Sheet.

3
A vacuum filtering apparatus (Technique 11E) can also be used; the filtering procedure will be
more rapid, but more precipitate may pass through the filter paper.
4
Whatman No. 42 and Fisherbrand Q2 filter papers are both fine-porosity filter papers; a fine-
porosity filter paper is used to reduce the amount of precipitate passing through the filter.

126 Limiting Reactant

exp08.qxd 11/15/13 10:29 AM Page 127

Ken Karp

Figure 8.2 Gravity filtration is used to

filter finely divided precipitates.

From the following two tests (Figure 8.3) you can determine the limiting reactant in B. Determination
the original salt mixture. Some cloudiness may appear in both tests, but one will show of the Limiting
a definite formation of precipitate. Reactant
1. Clarify the supernatant. Centrifuge the two collected supernatant samples from
Part A.4.
2. Test for excess C2O4 2–. Add two drops of (test reagent) 0.5 M CaCl2 to the
supernatant liquid in test tube 1. If a precipitate forms, the C2O4 2– is in excess and
Ca2+ is the limiting reactant in the original salt mixture.
3. Test for excess Ca2+. Add two drops of (test reagent) 0.5 M K2C2O4 to the
supernatant liquid in test tube 2. If a precipitate forms, the Ca2+ is in excess and
C2O4 2– is the limiting reactant in the original salt mixture.
An obvious formation of precipitate should appear in only one of the tests.
Repeat for Trial 2.

Figure 8.3 Testing for the excess (and the limiting) reactant

Experiment 8 127
exp08.qxd 11/15/13 10:29 AM Page 128

Disposal: Dispose of the calcium oxalate, including the filter paper, in the
Waste Solids container. Dispose of the waste solutions in the Waste Liquids
container.

CLEANUP: Rinse each beaker with small portions of warm water and discard in the
Waste Liquids container. Rinse twice with tap water and twice with deionized water
and discard in the sink.

The Next Step All reactions other than decomposition reactions have limiting reactants! From the
combustion of fossil fuels to the many integrated chemical processes of biochemical
reactions in living organisms, there is one reactant that limits the process. For exam-
ples, what is the limiting reactant in the combustion of gasoline in the cylinder of an
engine? What is the limiting reactant in the eutrophication of a body of water? What is
the limiting reactant in making bread rise? What is the limiting reactant in the precipi-
tation of a salt? Research the limiting reactant concept in upcoming experiments.

NOTES AND CALCULATIONS

128 Limiting Reactant

exp08.qxd 11/15/13 10:29 AM Page 129

Experiment 8 Prelaboratory Assignment

Limiting Reactant
Date __________ Lab Sec. ______ Name ____________________________________________ Desk No. __________
1. The limiting reactant is determined in this experiment.
a. What are the reactants (and their molar masses) in the experiment?

b. How is the limiting reactant determined in the experiment?

2. Experimental Procedure, Part A.2. What is the procedure and purpose of “digesting the precipitate”?

3. Two special steps in the Experimental Procedure are incorporated to reduce the loss of the calcium oxalate precipitate.
Identify the steps in the procedure and the reason for each step.

Experiment 8 129
exp08.qxd 11/15/13 10:29 AM Page 130

4. a. A sample of a CaCl2•2H2O/K2C2O4•H2O solid salt mixture is dissolved in ~150 mL of deionized water previously
adjusted to a pH that is basic. The precipitate, after having been filtered, was air-dried and weighed. Data for Trial 1
were obtained as shown. Complete the following table. (See Report Sheet.) Record calculated values with the cor-
rect number of significant figures.

A. Precipitation of CaC2O4•H2O from the Calculation Zone

Salt Mixture

3. Mass of salt mixture (g) ___________

0.879 Data Analysis, 1.
4. Mass of filter paper (g) ___________
1.896
5. Mass of filter paper and CaC2O4•H2O (g) ___________
2.180
6. Mass of air-dried CaC2O4•H2O (g) ___________

B. Determination of Limiting Reactant

Data Analysis, 3.
1. Limiting reactant in salt mixture CaCl2•2H2O
___________
2. Excess reactant in salt mixture ___________

Data Analysis

1. Moles of CaC2O4•H2O precipitated (mol)

Show calculation. ___________ Data Analysis, 4.
2. Moles of limiting reactant in salt mixture (mol)
See equation 8.1. ___________
3. Mass of limiting reactant in salt mixture (g)
Show calculation. ___________
4. Mass of excess reactant in salt mixture (g)
Equals mass of salt mixture minus mass of limiting reactant. Data Analysis, 5.
Show calculation. ___________
5. Percent limiting reactant in salt mixture (%)
Show calculation. ___________
6. Percent excess reactant in salt mixture (%) ___________

4. b. For Trials 2 and 3, the percent CaCl2•2H2O in the mixture was 39.7% and 28.4% respectively.
a. What is the average percent of CaCl2•2H2O in the sample? Data Analysis, B.

b. What are the standard deviation and the relative standard deviation (%RSD) for the percent of CaCl2•2H2O in
the sample? Data Analysis, C and D.

130 Limiting Reactant

exp08.qxd 11/15/13 10:29 AM Page 131

Experiment 8 Report Sheet

Limiting Reactant
Date __________ Lab Sec. ______ Name ____________________________________________ Desk No. __________

A. Precipitation of CaC2O4•H2O from the Salt Mixture

Unknown number ______________________ Trial 1 Trial 2

1. Mass of beaker (g) ______________________ ______________________

2. Mass of beaker and salt mixture (g) ______________________ ______________________

3. Mass of salt mixture (g) ______________________ ______________________

4. Mass of filter paper (g) ______________________ ______________________

5. Mass of filter paper and product after air-dried

or oven-dried (g) ______________________ ______________________

6. Mass of dried product (g) ______________________ ______________________

7. Formula of dried product ______________________ ______________________

B. Determination of Limiting Reactant

1. Limiting reactant in salt mixture (write complete formula) ______________________

2. Excess reactant in salt mixture (write complete formula) ______________________

Data Analysis

1. Moles of CaC2O4•H2O (or CaC2O4) precipitated (mol) ______________________* ______________________

2. Moles of limiting reactant in salt mixture (mol)

• formula of limiting hydrate _______________ ______________________ ______________________

3. Mass of limiting reactant in salt mixture (g) ______________________ ______________________

4. Mass of excess reactant in salt mixture (g)

• formula of excess hydrate _______________ ______________________ ______________________

5. Percent limiting reactant in salt mixture (%) ______________________ ______________________

6. Percent excess reactant in salt mixture (%) ______________________ ______________________

7. Mass of excess reactant that reacted (g) ______________________ ______________________

8. Mass of excess reactant, unreacted (g) ______________________ ______________________

*Show calculations for Trial 1 on next page.

Experiment 8 131
exp08.qxd 11/15/13 10:29 AM Page 132

Show all calculations fot Trial 1. See Data Analysis, A

Laboratory Questions
Circle the questions that have been assigned.
1. Part A.2. If the step for digesting the precipitate were omitted, will the reported “percent limiting reactant” in the salt
mixture be too high, too low, or unaffected? Explain.
2. Part A.3. A couple of drops of water were accidentally placed on the properly folded filter paper before its mass was
measured. However, in Part A.6, the CaC2O4•H2O precipitate and the filter paper were dry. As a result of this sloppy
technique, will the mass of the limiting reactant be reported too high, too low, or remain unaffected? Explain.
3. Part A.5. Because of the porosity of the filter paper some of the CaC2O4•H2O precipitate passes through the filter paper.
Will the reported percent of the limiting reactant in the original salt mixture be reported too high or too low? Explain.
4. Part A.5. Excessive quantities of wash water are added to the CaC2O4•H2O precipitate. Will the mass of the
CaC2O4•H2O be reported too high, too low, or remain unaffected? Explain.
5. Part A.6. The CaC2O4•H2O precipitate is not completely air-dried when its mass is determined. Will the reported mass
of the limiting reactant in the original salt mixture be reported too high or too low? Explain.
6. Part A.6, 7. The drying oven, although thought (and assumed) to be set at 125°C, had an inside temperature of 84°C.
How will this error affect the reported percent by mass of the limiting reactant in the salt mixture . . . too high, too low,
or unaffected? Explain.
7. Part A.4 and Part B. In a hurry to complete the experiment, Anna withdrew two volumes of solution from Part A.2
before the precipitate had settled. As a result, what dilemma might she have encountered in Part B? Explain.
8. Part B.2. A reagent bottle on the shelf labeled 0.5 M NaCl was used in place of the 0.5 M CaCl2. Assuming C2O42– to
be in excess, what would be observed as a result of using this wrong reagent in this test? Explain.

132 Limiting Reactant