AP* Chemistry Big Idea 1, Investigation 3

Gravimetric Analysis of Calcium

and Hard Water
Introduction
In certain areas of the country, the presence of hard water poses significant problems in water
supply systems. Various water softening techniques are used to remove the cations responsible for
water hardness. This investigation involves the application of gravimetric analysis to test samples
for the amount of water hardness and calcium ions.

Concepts
• Water hardness • Double replacement reactions
• Gravimetric analysis • Stoichiometry

Background
Water from natural sources may contain a number of dissolved substances. The amount and nature
of these dissolved substances varies depending on the geography of the area and the journey the
water has taken. As water travels through the ground or over the surface of the land, it can dissolve
naturally occurring minerals. As minerals dissolve in the water, the compounds separate into their
respective cations and anions. Common cations in water include Na+, Ca2+, Mg2+, and Fe3+, while the
principal anions in water are Cl−, HCO3−, NO3−, and SO42−. The main ions contributing to water hard-
ness are Ca2+, Mg2+ and, to a lesser extent, Fe3+. Their presence makes it difficult for soaps to lather
and also causes a “scum” to form. Equation 1 (where R is a long hydrocarbon chain) shows the pre-
cipitation reaction between alkyl sulfate anions in a typical soap with calcium ions in hard water.
The main problem due to water hardness in industrial pipes or boilers is the buildup of solid CaCO3,
which precipitates out and causes thick deposits to form in pipes and other appliances.
Ca2+(aq)  +  2ROSO3−(aq)  →  Ca(ROSO3 )2(s) Equation 1
Soap Soap scum
There are many different ways to “soften” water. One of the most common ways to remove ions is by
ion exchange. The ion exchange process uses a resin to replace some of the ions that cause hardness
with ions that do not. Hardness is commonly measured in units of grains per gallon or milligrams per
liter (also known as parts per million), and is classified by the U.S. Department of the Interior and the
Water Quality Association as follows:

Classification mg/L or ppm grains/gal

Soft 0–17.1 0–1
Slightly hard 17.1–60 1–3.5
Moderately hard 60–120 3.5–7.0
Hard 120–180 7.0–10.5
Very Hard 180 and over 10.5 and over

Although several ions contribute to water hardness, the units of mg/L or ppm are defined in terms of
the equivalent mass (milligrams) of CaCO3 that would be present per liter of water. In this investiga-
tion, gravimetric analysis will be used to precipitate and isolate solid CaCO3 from water samples and
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Gravimetric Analysis of Calcium and Hard Water 29

Gravimetric Analysis of Calcium and Hard Water continued

determine water hardness. Many municipal water treatment plants use soda ash (sodium carbonate,
Na2CO3 ) and lime (calcium hydroxide, Ca(OH)2 ) to chemically remove calcium and magnesium ions,
respectively, from hard water.

Experiment Overview
The purpose of this advanced inquiry lab is to investigate the suitability of gravimetric analysis
for determining the amount of water hardness in the form of calcium carbonate, CaCO3, in various
water samples. Six samples, representing a wide range of potential water hardness, from 50 ppm to
500 ppm, will be analyzed by various student groups as part of a cooperative class investigation to
determine the accuracy and sensitivity of gravimetric analysis for water hardness testing. Note that
all water samples have been concentrated by a factor of 100 for the purpose of quantitative analysis.
The lab begins with an introductory activity to develop skill in the calculations and techniques of
gravimetric analysis, in particular, quantitative transfer and vacuum or gravity filtration. The pre-
cipitation reaction involves preparing and combining solutions of Na2CO3 and CaCl2. The balanced
chemical equation for this reaction predicts the amount of precipitate that will be formed. Careful
isolation, drying and weighing of the precipitate will confirm the calculations and the percent yield.
The procedure provides a model for guided-inquiry design of the cooperative class investigation
described above. Antacid tablets may provide an opportunity for further inquiry—the use of gravi-
metric analysis to determine the amount of calcium in an over-the-counter medication.

Pre-Lab Questions
1. D
 efine the term gravimetric analysis. Describe the procedure used in this activity, and identify
two other common examples of gravimetric analysis.
2. W
 rite the balanced chemical equation for the reaction between calcium chloride and sodium
carbonate.
3. Calculate the number of moles of each reactant in the Introductory Activity (see steps 1 and 2).
Identify the limiting reactant in the reaction and determine the theoretical amount of CaCO3 that
should be produced.
4. As noted in the Background section, hardness levels are calculated by assuming that all the “hard”
metal ions come from dissolved calcium carbonate and are reported in mg CaCO3/L. Calculate the
equivalent water hardness in mg CaCO3/L for a calcium chloride solution containing 0.1 M Ca2+ ions.

Materials (for each lab group)

Calcium chloride, anhydrous, CaCl2, 2 g Filter flask, 250-mL
Hard water samples, 20 mL, 2 Filter paper, 3
Sodium carbonate solution, Na2CO3, 0.5 M Funnel, Büchner and rubber adapter
Sodium carbonate, anhydrous, Na2CO3, 2 g Graduated cylinder, 50-mL
Water, deionized or distilled Spatula
Antacid tablets (optional) Vacuum filtration apparatus setup
Balance, 0.001-g precision (shared) Wash bottle
Beakers, 150-mL, 3 Watch glasses, 2
Drying oven (shared) Weighing dishes, 2

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30 Flinn Scientific Advanced Inquiry Labs for AP* Chemistry

 Gravimetric Analysis of Calcium and Hard Water continued

Safety Precautions
Sodium carbonate is irritating to body tissues. Anhydrous calcium chloride is moderately toxic by inges-
tion and generates a great deal of heat when dissolved in water. Avoid contact of all chemicals with eyes
and skin. Antacid tablets used in the lab are considered laboratory chemicals and may not be removed
from the lab. Do not taste or ingest any materials in the chemistry lab. Wear chemical splash goggles,
chemical-resistant gloves, and a chemical-resistant apron. Wash hands thoroughly with soap and water
before leaving the laboratory. Please follow all laboratory safety guidelines.

Introductory Activity
Precipitation Reaction and Vacuum Filtration
1. W
 eigh 2.5 g of sodium carbonate and place in a clean, dry 150-mL beaker. Record the precise mass
and dissolve the solid in 20 mL of deionized or distilled water.
2. W
 eigh 2.0 g of calcium chloride and place in a clean, dry 150-mL beaker. Record the precise mass
and dissolve the solid in 20 mL of deionized or distilled water.
3. Combine the two solutions by slowly adding the sodium carbonate solution to the calcium chlo-
ride solution. Record all observations about the reaction.
4. Separately weigh a piece of filter paper and a watch glass and record their masses.
5. S
 et up a vacuum filtration apparatus as shown in Figure 1. The second filter flask is used to pre-
vent back-up of water from the aspirator to the filter flask when the vacuum is released.

Heavy Rubber Tubing with

Aspirator Tubing Pinch Clamp

Büchner Funnel
 or help in setting up a vacuum filtration and tips for
F
carrying out the procedure, please see the following
Rubber
Adapter
How-To Videos on the Flinn Scientific website under
Teacher Resources: “How to Set Up a Vacuum Filtration”
and “How to Perform a Vacuum Filtration.” (flinnsci.com)

Thick-Walled
Filter Flasks

Figure 1.  How to Set Up a Vacuum Filtration

6. Isolate the precipitate by vacuum filtration. Careful transfer techniques are essential for
accurate results! Precipitate may also be collected by gravity filtration.
7. Place the watch glass and filter paper containing precipitate in a lab oven to dry at 100 °C for
10–20 minutes. Monitor and carefully break up the solid with a spatula to ensure complete drying.
8. Calculate the percent yield of calcium carbonate.

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Gravimetric Analysis of Calcium and Hard Water 31

Gravimetric Analysis of Calcium and Hard Water continued

Guided-Inquiry Design and Procedure

Accuracy and Sensitivity of Gravimetric Analysis to Determine Water Hardness
Form a working group with other students and discuss the following questions.
1. The ideal precipitate in a gravimetric analysis procedure should be insoluble and have a known
composition. Using reference texts such as The Merck Index or the Handbook of Chemistry and
Physics, look up the properties of calcium carbonate and discuss its advantages and possible
disadvantages for gravimetric analysis of calcium.
2. Based on solubility rules, what ions in water might interfere with the analysis of calcium ions by
precipitation of calcium carbonate?
3. Precipitate particles in gravimetric analysis must be large enough to be collected by filtration—
smaller particles may pass through or clog the filter. Discuss how the following techniques will
help prevent product loss and ensure product purity in a gravimetric procedure.
• Add the precipitant slowly with vigorous mixing.
• “Digest” the precipitate by allowing it to stand in contact with the solution and/or heating the
mixture for 10–15 minutes.
• Rinse the precipitate with a small amount of water after filtration.
 ix water samples containing known concentrations of calcium chloride are available for analysis as
S
part of a cooperative class activity. Each student group should analyze two different samples. The
recommended sample volume for the precipitation reaction is 20 mL. Complete the table below with
the results of the calculations from Questions 4–6 below.

Theoretical
Volume of 0.5 M
Moles of Ca2+ in Amount Theoretical Water
Sample [CaCl2], M Na2CO3
20 mL of Solution of CaCO3 Hardness, mg/L
(20% excess)
Precipitate
1 0.400 0.008 0.801 g 19.2 mL (20) 400 mg/L
2 0.200
3 0.500
4 0.100
5 0.050
6 0.300

4. Calculate the number of moles of Ca2+ ion in 20 mL of each solution and the theoretical amount
of CaCO3 that can be obtained by reacting 20 mL of each solution with excess sodium carbonate.
Enter the results in the table.
5. Excess sodium carbonate solution (precipitant) is recommended to ensure that all of the cal-
cium ions in solution are converted to product. For each sample, determine the volume of 0.5 M
sodium carbonate solution that provides the stoichiometric number of moles of Na2CO3 needed
to react completely with the CaCl2 solution. Multiply the result by 1.2 to provide a 20% excess,
and enter the results in the table.
6. Calculate the theoretical water hardness in mg CaCO3/L for each water sample. Recall that each
sample has been concentrated by a factor of 100 to provide the solution shown in column 2.
The calculation for sample 1 is shown below as a guide:
(0.801 g CaCO3 /0.020 L)  ×  (1000 mg/g)  × (1/100) =  400 mg CaCO3 /L

Note that the factor 1/100 accounts for the concentration of the original water sample to the final
analyzed volume of 20 mL.
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32 Flinn Scientific Advanced Inquiry Labs for AP* Chemistry
 Gravimetric Analysis of Calcium and Hard Water continued

7. W
 rite a detailed, step-by-step procedure for analyzing the concentration of calcium in the water
samples. Include the reagents needed, the glassware and equipment that will be used, and the
appropriate measurements and observations that must be made.
8. Review the hazards of the chemicals used in the procedure and write appropriate safety
precautions that must be followed during the experiment.
9. Carry out the procedure and record the results in an appropriate data table.
10. Repeat the analysis as needed to check for reproducibility.

Analyze the Results

Calculate the percent yield of calcium carbonate and determine the experimental water hardness in
mg/L for each sample. Classify the water hardness of each sample according to the criteria established
by the U.S. Department of the Interior and the Water Quality Association (see the Background section).
Compile the class data for all the samples that were analyzed and compare the accuracy and sensitivity
of the gravimetric analysis procedure over the range of possible water hardness from 50 to 500 mg/L.

Opportunities for Inquiry

Gravimetric Analysis to Determine the Mass of Calcium Ion in an Antacid Tablet
The amount of calcium in an antacid tablet may also be determined using gravimetric analysis. Note
that antacid tablets contain binders and other inert ingredients or additives. Design a procedure to
dissolve and separate the calcium carbonate from the binders in the tablet and analyze the amount
of calcium.

© 2015, Flinn Scientific, Inc. All Rights Reserved. Reproduced for one-time use with permission from Flinn Scientific, Inc. Batavia, Illinois, U.S.A. No part of this mate-
rial may be reproduced or transmitted in any form or by any means, electronic or mechanical, including, but not limited to photocopy, recording, or any information
storage and retrieval system, without permission in writing from Flinn Scientific, Inc.

Gravimetric Analysis of Calcium and Hard Water 33

Gravimetric Analysis of Calcium and Hard Water continued

AP Chemistry Review Questions

Integrating Content, Inquiry and Reasoning
Copper(II) chloride (CuCl2; 0.98 g) was dissolved in water and a piece of aluminum wire (Al; 0.56 g)
was placed in the solution. The blue color due to copper(II) chloride soon faded and a red precipi-
tate of solid copper was observed. After the blue color had disappeared completely, the leftover
aluminum wire was removed from the solution and weighed. The mass of the leftover aluminum wire
was 0.43 g.
1. Calculate the number of moles of (a) copper(II) chloride and (b) aluminum that reacted.

2. W
 hat is the mole ratio of copper(II) chloride to aluminum metal? Express this to the nearest
whole number ratio.

3. W
 hat happened to the aluminum metal that was consumed in this reaction? Write the formula of
the most probable aluminum-containing product.

4. W
 rite a balanced chemical equation for the single replacement reaction of copper(II) chloride
with aluminum.

© 2015, Flinn Scientific, Inc. All Rights Reserved. Reproduced for one-time use with permission from Flinn Scientific, Inc. Batavia, Illinois, U.S.A. No part of this mate-
rial may be reproduced or transmitted in any form or by any means, electronic or mechanical, including, but not limited to photocopy, recording, or any information
storage and retrieval system, without permission in writing from Flinn Scientific, Inc.

34 Flinn Scientific Advanced Inquiry Labs for AP* Chemistry