Phillips-Rahman 1

Introduction

According to a U.S. geological survey, hard water is found in over 85% of

the country. From household issues like cleaning in the kitchen or bathroom and

heating in pipes to treatment concerns at municipal water plants, hard water can

be found to play a significant role (Braff). Moreover, hard water continues to be a

national problem that requires immediate attention and more effective treatment

methods.

Figure 1. Water Hardness Levels in the U.S. (Mesquita)

Figure 1 above shows the map of the concentration of hard water

throughout the United States, measured in grains per gallon (GPG) of CaCO 3. It

can be seen that hard water poses a concern in most regions of the country,

particularly the Midwest.

Considering the fact that hard water is so common location-wise and

utilized everyday in various ways, it is imperative that methods to treat it are

studied and advanced upon. One way municipal water plants can soften water

containing hardness minerals such as calcium and magnesium is by gravimetric

analysis, as performed in this experiment. Since gravimetric analysis is known to

 Phillips-Rahman 2

be an accurate method to remove hard minerals from water, it was sensible to

apply this technique in measuring the hardness of water in the form of calcium

carbonate.

One example of how the precipitate formed by hard water can cause

problems is the formation of scale in water pipes. The scale buildup restricts the

flow of water through hot water vessels such as pipes and boilers and sharply

reduces their operating efficiency (Mesquita). Therefore, it is necessary for water

utilities to treat hard water effectively before it can reach homes and result in

these inconveniences.

The central objective of this research was to take the basic fundamental

steps to discovering the properties of the main constituent in hard water: calcium.

By analyzing this element through the process of gravimetric analysis in various

water samples at different concentrations, this objective was successfully

completed. In particular, five different samples of water at assigned molarities

were made into solutions containing calcium chloride and a precipitating agent,

sodium carbonate. After the precipitate of calcium carbonate was formed and

isolated in vacuum filtration, the samples were dried in a lab oven and weighed.

Using the mass of the precipitate, the water hardness of each sample and type of

water was found.

With a greater understanding of the characteristics of such a crucial

element found in water, municipal water plants may discover new ways to treat

hard water. Better methods than the ones currently utilized in measuring water

hardness such as titration procedures can be applied, and household

 Phillips-Rahman 3

problems like scum, scale, and sludge formation can be prevented. As a whole,

this topic of research is extremely relevant to the modern world. The importance

of water and its abilities to clean and heat homes will always remain prevalent in

the function of everyday life. Delving into and comprehending the fundamental

aspects of gravimetric analysis in relation to determining water hardness is only

the first step to developing and prospering as a community.

Review of Literature

The purpose of this experiment was to analyze the accuracy of gravimetric

analysis for determining water hardness in the form of CaCO 3. Water hardness is
 Phillips-Rahman 4

defined in terms of the mass of CaCO3 that would be present per liter of water.

Although several ions contribute to water hardness, Ca 2+ and Mg2+ are found to

be the main ones. Their presence makes it difficult for soaps to lather and can

also cause a scum to form. In fact, the main problem due to water hardness in

industrial pipes or boilers is the buildup of solid CaCO 3, which precipitates out

and causes scale to form in pipes and other appliances (Gravimetric Analysis of

Calcium and Hard Water). There are several methods in use to measure the

hardness of water, such as titration procedures and gravimetric analysis. This

research utilized gravimetric analysis to isolate, dry, and weigh the precipitate

formed in various samples of water to find the mass of CaCO 3 in each.

Appropriate calculations were then performed using this mass to finally

determine percent yield and water hardness.

Gravimetric analysis can be used to quantify a variety of substances, but

in this experiment the focus was on hard water. Water from natural sources may

contain a number of dissolved substances, but the amount and nature of these

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, and as these minerals dissolve

in the water, the compounds separate into their respective cations and anions

(Gravimetric Analysis of Calcium and Hard Water). Cations are positively

charged chemical ions, and hard water is defined as water containing Ca 2+ or

Mg2+ cations (Casiday and Frey). Hard water leaves a residue on the hands,

dishes, bathtubs, or sinks. This residue is commonly known as soap scum and
 Phillips-Rahman 5

can feel slimy and leave streaks of mineral deposits wherever the water is run

(Perlman). The reaction between soap and calcium causes the formation of this

residue. Most soaps contain baking soda, also known as NaHCO 3.

Ca2+ (aq) + 2HCO3- (aq) CaCO3 (s) + H2O (l) + CO2 (g)

Figure 2. Reaction Between Ca2+ and HCO3-

Figure 2 illustrates the balanced chemical reaction of Ca 2+, an element

found in hard water, and HCO3-, an ingredient found in baking soda and soap.

The reactants, aqueous Ca2+ and aqueous HCO3-, are displayed on the reactants

side of the reaction (left). Aqueous simply means the reactant or product contains

water and is not solid. Solid CaCO3, liquid H2O, and gaseous CO2 are listed on

the products side of the reaction (right). Since CaCO 3 also referred to as scale

is solid, it is insoluble. This means it can build up in areas where the reaction

occurs, like water pipes.

Table 1
Water Hardness Levels
Classification mg/L or ppm of CaCO3 grains/gal of CaCO3

Soft 0 - 17.1 0-1

Slightly hard 17.1 - 60 1.0 - 3.5

Moderately hard 60 - 120 3.5 - 7.0

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Hard 120 - 180 7.00 - 10.5

Very hard 180 and over 10.5 and over

Table 1 above lists the different classifications of water. The amount of

CaCO3 is listed in milligrams per liter (or ppm, parts per million) and grains per

gallon (Gravimetric Analysis of Calcium and Hard Water).

Table 2
Standard Water Hardness Levels
Source of Water ppm of CaCO3

Typical Swimming Pool Water 200 - 300

Pontiac Groundwater 292

Lake St. Clair/Upper Detroit River Water 97

Treated Ypsilanti Groundwater 70

Table 2 shows the representative water hardness levels for a typical

swimming pool, Pontiac groundwater, Lake St. Clair water, and Ypsilanti treated

groundwater in Michigan. According to Table 1 and Table 2, typical swimming

pool water can be considered very hard, meaning it contains over 180 milligrams

of CaCO3 per liter. Groundwater from Pontiac can also be classified as very hard,

but Lake St. Clair water and treated Ypsilanti groundwater count as moderately

hard (Wisler, Stramel, and Laird).

Hard water does not pose a serious threat to health; however, the ions in

hard water can engage in reactions that leave insoluble mineral deposits. The

scale that precipitates out of these reactions coats the vessels in which water is

heated, producing the mineral deposits that can be seen on dishes or in the

bathroom. In small quantities, the deposits are not harmful, but they can be
 Phillips-Rahman 7

frustrating to remove. As the buildup of scale in pipes increases, however, the

efficiency of heat transfer can decrease. Water is not heated as evenly or quickly

if scale starts to coat the insides of water pipes. A major financial problem caused

by hard water is the inefficiency of industrial-sized water boilers. If it takes longer

for heat to transfer due to the scale, the price of a power bill can skyrocket

(Casiday and Frey). Long-term movement of hard water through pipes can also

cause scale buildup, leading to lower water pressure and less water movement.

For example, cholesterol can clog up blood vessels in the human body, resulting

in a smaller inside diameter. In the same way, water pipes can gradually close

up. Finally, the hardness minerals in the water can wear down fabrics and

clothes. Furthermore, hardness is a property of water that is not a health

concern, but it can be a nuisance. Hard water can produce mineral buildup in

plumbing, fixtures, and water heaters, and cause poor performance of soaps and

detergents (Perlman).

The most convenient way to soften hard water is to remove the Ca 2+ or

Mg2+ ions. One of the most common household ways to remove ions is by ion

exchange. In this process, a resin is used to replace some of the ions that cause

hardness in water with ions that do not (Gravimetric Analysis of Calcium and

Hard Water). Ion-exchange devices consist of a bed of plastic (polymer) beads

covalently bound to anion groups, such as -COO -. The negative charge of these

anions is balanced by Na+ cations attached to them. When water containing Ca2+

and Mg2+ is passed through the ion exchanger, the Ca 2+ and Mg2+ ions are more

attracted to the anion groups than the Na + ions. Hence, they replace the Na+ ions
 Phillips-Rahman 8

on the beads, and the Na+ ions (which do not form scale) replace them in the

water (Casiday and Frey).

Figure 3. Ion-Exchange Process (Casiday and Frey)

In the figure above, the process of ion-exchange is shown. When hard tap

water passes through the ion exchanger (left), the Ca 2+ ions from the tap water

replace the Na+ ions in the ion exchanger. The softened water, containing Na +

ions in place of Ca2+ ions, can be collected for household use.

Unfortunately, many people with high blood pressure or other health

problems must restrict their intake of sodium. Because water softened by this

type of ion exchange contains many Na+ ions, people with limited sodium intakes

should avoid drinking water that has been softened this way. Moreover, the ion

exchange process is not the most ideal way to soften hard water. Many municipal

water plants utilize a process known as the lime-soda process to treat hard

water. Ion-exchange reactions, which result in the formation of an insoluble

precipitate, are the basis of this procedure. The water is treated with a

combination of slaked lime, Ca(OH)2, and soda ash, Na2CO3. Calcium

 Phillips-Rahman 9

precipitates as CaCO3, and Mg2+ precipitates as Mg(OH)2. These solids can be

collected, thus removing the scale-forming cations from the water supply.

Mg2+ (aq) + 2OH- (aq) Mg(OH)2 (s)

Figure 4. Precipitation of Mg(OH)2

In the figure above, an example reaction for the lime-soda process is

portrayed. Since Ca(OH)2 of slaked lime is moderately soluble in water, it can

dissociate to give one Ca2+ ion and two OH- ions for each unit of Ca(OH)2 that

dissolves. The OH- ions react with Mg2+ ions in the water to form the insoluble

precipitate. Calcium ions are unaffected by this reaction, and so they are not

included in the net ionic reaction shown. They are removed by the separate

reaction with CO32- ions from the soda ash (Casiday and Frey). Another less

commonly utilized method to treat hard water is gravimetric analysis.

Gravimetric analysis is used to determine the amount of a substance in a

sample. This is done by reaction of the substance with a precipitating agent, and

then the solid product or precipitate obtained is massed (Gravimetric Analysis of

Calcium and Hard Water). A precipitate is an insoluble substance, meaning it

cannot be dissolved in water. The principle behind gravimetric analysis is that the

mass of an ion in a pure compound can be determined and then used to find the

mass percent of the same ion in a known quantity of an impure compound. In

order for the analysis to be accurate, certain conditions must be met: the ion

being analyzed must be completely precipitated, the precipitate must be a pure

compound, and the precipitate must be easily filtered (Wired Chemist). There are

several different methods of gravimetric analysis, but they all rely on some final
 Phillips-Rahman 10

determination of mass as a means of quantifying an analyte the chemical

substance to be analyzed. Since mass can be measured with greater accuracy

than almost any other fundamental property, gravimetric analysis is known to be

a very accurate class of analytical methods available. Although gravimetric

analysis has proven to be extremely reliable, it is a very tedious and time-

consuming procedure (Fisherman and Friedman). Moreover, alternate methods

to gravimetric analysis tend to be applied in laboratories today to analyze

samples.

To satisfy the condition that a precipitate with a known composition be

formed, CaCO3 was used in this experiment. Calcium carbonate is considered

virtually insoluble in water and is thus an ideal candidate for the gravimetric

determination of Ca2+ ions. It has a stable condition but exists as a potential

hexahydrate. A hexahydrate is a compound that contains six molecules of water.

Heating the precipitate to approximately 100C ensured that the solid was

thoroughly dried to remove the waters of hydration so the percent yield

determination was accurate (Gravimetric Analysis of Calcium and Hard Water).

The precipitating agent in gravimetric analysis must be added slowly to

ensure even mixing and avoid local areas of supersaturation, which would lead to

small particles or even a colloidal solution. A supersaturated solution is an

unstable solution that contains more solutes, and a colloid is a solid made up of

particles having diameters less than 10-4 cm. With time, supersaturation is

relieved by precipitation of the excess solute (in this experiment, Na 2CO3). To

increase the particle size of a precipitate so it is not filterable, the relative

 Phillips-Rahman 11

supersaturation during the precipitate formation should be minimized. Digestion

in gravimetric analysis is a process which involves heating the solid for a certain

period of time. Heating and then cooling the mixture essentially promotes

recrystallization of the solid, which leads to larger crystal or particle growth and

also helps remove impurities that might be adsorbed on the surface. Adsorption

is a process that occurs when a substance such as a solid, liquid, or gas, is held

on the surface of a solid (Texas A&M University). After the addition of the

precipitating agent to the solution of the ion under analysis, nucleation occurs.

During nucleation, atoms join together, and it is from these clumps of atoms that

the crystals which form the precipitate will grow. As the precipitate forms, ions

from the solution which are in excess at this point congregate around the

nuclei, or joined atoms.

Figure 5. Colloidal Solution and Adsorption (Texas A&M University)

For example, if HCl (aq) was added very slowly to a solution of AgNO 3,

AgCl nuclei would form and Ag + ions (which would be in excess relative to Cl-
 Phillips-Rahman 12

ions) would congregate around them. In addition to the primary adsorbed Ag + ion,

there would be some NO3 ions aggregating further from the AgCl nucleus. These

are counterions and tend to aggregate around the [AgCl:Ag] + center because

these centers have a net positive charge (excess Ag +), and an additional

negative charge is required to maintain electrical neutrality. The counterions are

held less tightly than the primary adsorbed ions, and the counterion layer is

somewhat diffused and contains ions other than those of the counterions. These

layers of charges are known as the electric double layer.

To summarize thus far, gravimetric analysis is much slower than

instrumental techniques to determine the hardness of water because samples

may have to be extensively treated to remove interfering substances (CHAPTER

XV: GRAVIMETRIC METHODS). According to a lab manager at the Port Huron

Wastewater Treatment Plant, the main obstacle for attempting to estimate

hardness gravimetrically is that there may be a lot of other mineral ions present

besides the calcium and magnesium (Troy). Instrumental techniques tend to

allow simultaneous determination of several constituents, while gravimetric

analysis deals with one sample at a time and is a quite tedious process.

However, there are instances when gravimetric analysis is the only suitable

option, so this method is still in use. Although time-consuming, this method can

produce extremely accurate results, contrasting previous research that claim it is

not as efficient as other methods such as titration procedures (Fisherman and

Friedman).
 Phillips-Rahman 13

Previous research has been conducted on the effect of hard water on the

mortality rate of cardiovascular disease or stroke. In 2010, researchers Lina J.

Leurs, Leo J. Schouten, Margreet N. Mons, R. Alexandra Goldbohm, and Piet A.

van den Brandt from the Environmental Health Perspectives collected detailed

information about dietary habits from thousands of men and women in the

Netherlands and calculated the water hardness levels for each postal code the

subjects were from. The researchers were affiliated with Maastricht University,

GROWSchool for Oncology and Developmental Biology, and the Department of

Epidemiology in Maastricht (Leurs et al.). These researchers then observed and

kept track of the Ischemic heart disease (IHD) mortality or stroke mortality rate

among the subjects. Their experiment found no evidence for an overall significant

association between tap water hardness, Mg2+ and Ca2+ concentrations, and IHD

or stroke mortality. This relates to the experiment testing the accuracy of

gravimetric analysis in determining the amount of CaCO 3 in hard water because

the study questioned whether hard water would have a negative effect on the

health of common people. Although gravimetric analysis was not utilized in the

study and their hypothesis was rejected, the minerals predominantly determining

water hardness namely Mg2+ and Ca2+ remain of interest to the World Health

Organization and future research.

In 2010, student researchers Jarryd Campbell and Dan Peterson from

Concordia College, Minnesota, conducted an experiment in which the hardness

of water was determined using flame atomic absorbance spectrometry, an

alternative method to common and traditional titration methods. Typical titration

 Phillips-Rahman 14

methods involve human intervention, slowing down the process and limiting

efficiency. Flame atomic absorbance spectroscopy (AA) consists of the sample

being exposed to an open flame that breaks it down into its basic atomic

components. Then, light with a specific wavelength is sent through the desired

atom in the sample and its absorbance is measured and quantified. Three

samples of water were used: water from a local river, tap water, and water from

drinking fountains. Their research found that their hypothesis was indeed correct;

river water was much harder compared to tap water and water from drinking

fountains. They also compared their results to historical methods of determining

water hardness by EDTA (Ethylenediaminetetraacetic) titration methods, and

found that atomic absorbance was reliable and more efficient (Campbell and

Peterson). Although their experiment was aimed specifically at determining the

hardness of water using a different method other than gravimetric analysis, this

experiment still used the research. For instance, Campbell and Peterson tested

and found that local river water can be up to three times harder than tap water or

water from drinking fountains, so this experiment consisted of samples similar to

those three categories. The results obtained in this research were compared to

Campbell and Petersons results to see if river water was indeed significantly

harder than drinking water and if gravimetric analysis happened to be a more

accurate method to determine the amount of water hardness in various water

samples than both atomic absorbance and EDTA titration methods.

Conclusively, the purpose of the experiment was to investigate the

proficiency of gravimetric analysis in measuring the amount of CaCO 3 in hard

 Phillips-Rahman 15

water. Hard water is water that contains Ca2+ or Mg2+ cations and has not been

treated. There is a range of techniques to treat or soften hard water, from ion-

exchange reactions and devices to titration procedures. Gravimetric analysis is a

method that uses mass to quantify a substance. This type of analysis can be

time-consuming, but it is beneficial because it is one of the most accurate

methods available. Previous research has helped support the idea that

gravimetric analysis is effective, and that hard water does not have any

significant negative consequences in concerns to human health. Even more

previous research has shown that there are alternate methods found to be more

efficient than titration techniques, and this experiment investigated if gravimetric

analysis was one of them. All in all, it is important to know the hardness of water

when formulating a treatment plan. If water is not treated correctly, it can have a

harmful effect on appliances and lead to expensive bills.

 Phillips-Rahman 16

Problem Statement

Problem:

To determine the efficiency and effectiveness of gravimetric analysis when

measuring the amount of CaCO3 in hard water.

Hypothesis:

Gravimetric analysis will not be accurate in determining the amount of

CaCO3 in hard water.

Data Measured:

The independent variables in this experiment were the type of water

sample; the concentration of Ca2+, measured in moles per liter or molarity (M);

the amount of CaCl2 stock solution needed to dilute the water samples,

measured in milliliters; and the amount of excess Na 2CO3 added to each hard

water solution, measured in milliliters. Five different types of water samples were

tested: water from the Detroit River at Belle Isle in Detroit, Michigan; water from

the well water system in Lake Orion, Michigan; water from Lake Saint Clair at a

canal in Saint Clair Shores, Michigan; water from a swimming pool at Warren

Mott High School in Warren, Michigan; and distilled water bought from a store.

Concentrations of Ca2+ included 0.100 M, 0.200 M, 0.300 M, 0.400 M, and 0.500

M. Each sample of water was randomly assigned one of the five concentrations.

Calculations were done before conducting the experiment to determine how

 Phillips-Rahman 17

much CaCl2 stock solution and excess Na2CO3 solution were needed for each

sample of water. The dependent variables were the mass of the precipitated

sample which was CaCO3 measured in grams; the percent yield of the

precipitate, which is the ratio of the amount of substance produced to the amount

of substance expected to be produced; and water hardness, expressed in

milligrams of CaCO3 per liter of water. Fifteen trials (order randomized) were

conducted three trials for each sample of water. A one-sample t confidence

interval was appropriate for analyzing this experiments results because the true

water hardness for each water type was not known, but an interval could be

obtained from sample data that tried to estimate the true population mean.
 Phillips-Rahman 18

Experimental Design

Materials:

30 g calcium chloride anhydrous, CaCl2 (4) 1 L plastic containers

225 mL calcium chloride solution, CaCl2 (2) weighing dishes
30 g sodium carbonate anhydrous, Na2CO3 (3) 50 mL graduated cylinders
225 mL sodium carbonate solution, Na2CO3 (3) 250 mL beakers
(3) 20 mL distilled water samples (15) 5.5 cm filter paper
(3) 20 mL lake water samples (2) watch glasses
(3) 20 mL pool water samples 7 cm pipet
(3) 20 mL river water samples Glass stirring rod
(3) 20 mL well water samples Wash bottle with distilled water
Vacuum filtration setup (see Appendix A)Scoopula
Digital balance (0.001-g precision) Drying oven (100C)

Procedures:

Lab Preparation

1. Collect water samples from specified locations (see Appendix B),

one sample from each location. Store each sample in its own labeled 1 L
plastic container.

2. Randomize fifteen trials using TI-Nspire software. Randomly assign

concentrations to each type of water as well.

3. Clean all lab materials thoroughly by rinsing with distilled water.

4. See Appendix C for the amount of 2 M CaCl2 stock solution needed

to be diluted to prepare 100 mL of each sample of water. Measure this
amount out using a 50 mL graduated cylinder.

5. Pour the CaCl2 stock solution into a 250 mL beaker.

6. Mix the water sample and 2 M CaCl2 stock solution well with a
glass stirring rod.

7. Label the beaker with the name of the water sample and the
assigned molarity of the solution.

8. Repeat steps 3-7 for each trial.

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Precipitation Reaction

9. Use scoopula to measure out 2.5 g of Na2CO3 anhydrous and

place in a
clean, dry 250 mL labeled beaker.

10. Measure out 20 mL of distilled water using graduated cylinder and

pour into
beaker to dissolve Na2CO3 anhydrous. Mix solution thoroughly.

11. Use scoopula to measure out 2.0 g of CaCl 2 anhydrous and place
in a clean, dry 250 mL labeled beaker.

12. Measure out 20 mL of prepared solution from step 6 using a

graduated
cylinder and pour into beaker to dissolve CaCl 2 anhydrous. Mix solution
thoroughly.

13. Slowly add the Na2CO3 solution from step 10 to the CaCl2 solution
from step
12 and mix thoroughly. Record all observations about the reaction.

14. See Appendix D for the amount of excess Na 2CO3 solution needed
to
completely precipitate the Ca2+ ions in the CaCl2 solution. Use a
graduated cylinder to pour excess Na2CO3 into beaker. Mix thoroughly.

15. Repeat steps 9-14 for each trial.

Vacuum Filtration

16. Separately weigh a piece of filter paper and a watch glass. Record
their
masses.

17. See Appendix A to set up a vacuum filtration.

18. Slowly pour precipitate over filter paper.

19. Wash out any precipitate remaining in beaker with distilled water
and pour
over filter paper.

20. Pour any precipitate that seeped through the filter paper and
funnel into the
 Phillips-Rahman 20

flask back over the filter paper by using an extra Erlenmeyer flask.

21. Wash precipitate with distilled water.

22. Remove filter paper containing precipitate from funnel by using

scoopula
and place on watch glass.

23. Place the watch glass and filter paper with the precipitate in a lab
oven to
dry at 100C for 10-20 minutes.

24. Weigh dried precipitate on watch glass and record mass.

25. Calculate percent yield of CaCO3 to determine accuracy of

gravimetric
analysis and record (see Appendix E for sample calculations).

26. Calculate water hardness of water sample using mass found in

step 24 and
record (see Appendix F for sample calculations).

27. Clean all lab materials thoroughly by rinsing with distilled water.

28. Repeat steps 16-27 for each trial.

Diagram:

Figure 6. Vacuum Filtration Setup

 Phillips-Rahman 21

Figure 6 above shows a diagram of the filtration setup. Details for the

exact setup and all the materials needed can be found in Appendix A.

Data and Observations

Before conducting the experiment, 100 mL of solution had to be prepared

using CaCl2 solution and each sample of water. In addition, theoretical

calculations were performed. Each sample of water was randomly assigned a

molarity. In order to calculate the theoretical amount of CaCO 3 that would be

formed, the moles of Ca2+ in 20 mL of the prepared solution had to be found. The

formula used to calculate this is shown below:

mol
M=
L

Figure 7. Calculating Ca2+ Moles

In this formula, M represents the molarity to be achieved for each water

sample. The amount of Ca2+ ions in moles, which is represented by mol, is

divided by the volume of the solution, L. A sample calculation can be found in

Appendix D.

Next, the theoretical amount of CaCO3 that was formed by each sample of

water was found.

100.086 g Ca CO3
2+
1 mol CaCO 3
g CaCO 3=mol Ca
 Phillips-Rahman 22

Figure 8. Theoretical Amount of CaCO3 Precipitate

In the equation above, the sum of the moles present in 20 mL of prepared

solution and 2.0 g of CaCl2 anhydrous was multiplied by the theoretical mass of

CaCO3 present per mole of CaCO3. This result was interpreted as the theoretical

amount of CaCO3 precipitate to be formed by a water sample. A sample

calculation can be found in Appendix G.

In order to precipitate all the Ca2+ ions, excess Na2CO3 was added and

mixed into the prepared solution.

1L
1 mol Ca2 + 1.2
0.5 mol Na 2 CO 3
1 mol Na2 CO3
2+
Vof Na2 CO3 =mol Ca

Figure 9. Excess Na2CO3

In the equation above, the number of moles present in 20 mL of CaCl 2

solution was multiplied by moles of Ca2+ present per mole of Na2CO3. This result

was then multiplied by moles of Na2CO3 present per liter of solution. Finally, the

result was multiplied by 1.2 to provide a 20% excess. A sample calculation can

be found in Appendix D.

Lastly, the theoretical water hardness for each sample of water was

determined.

g CaCO 3 1000 mg 1000 mL 1

mgCa CO3 / L=
mL 1g 1L 100

Figure 10. Theoretical Water Hardness

In the equation above, the theoretical mass of the precipitate was

converted from g/mL to mg/L. The result was multiplied by the factor 1/100 to
 Phillips-Rahman 23

account for the fact that the sample analyzed was 100 times more concentrated

than the original water sample. A sample calculation can be found in Appendix F.

Table 3
Theoretical Calculations

Theoretical
Volume Theoretical
Hard Molarity Moles of Ca2+ Amount of
of 0.5 M Water
Water of CaCl2 in 20 mL CaCO3
Na2CO3 Hardness
Sample (M) Solution (mol) Precipitate
(mL) (mg/L)
(g)

Distilled
0.100 0.0200 2.00 5.00 445
Water

Lake
0.200 0.0220 2.20 10.0 441
Water

Well
0.300 0.0240 2.40 15.0 437
Water

River
0.400 0.0260 2.60 20.0 434
Water

Pool
0.500 0.280 2.80 24.0 438
Water

Table 3 lists the concentration of CaCl2 in each different water sample, the

moles of Ca2+ ions in 20 mL of prepared solution of each sample, and the

theoretical amount of CaCO3 precipitate formed by each sample. The volume of

excess 0.5 M Na2CO3 added to each solution is also given along with the

theoretical water hardness of each sample. Details pertaining the water samples

can be found in Appendix B.

 Phillips-Rahman 24

Table 4
Mass of CaCO3
Hard Water Sample

Distilled Lake Water Well River Pool

Trial Water Masses (g) Water Water Water
Masses (g) Masses (g) Masses (g) Masses (g)

1 1.4624 1.9294 1.3993 2.4135 2.7152

2 2.5559 2.0379 1.1551 1.2216 2.5907

3 1.8044 2.0503 3.7575 4.9560 2.6278

Average 1.9409 2.0059 2.1040 2.8637 2.6446

Standard
Deviation 0.55938 0.066512 1.4372 1.9075 0.063921

Table 4 displays the mass of the CaCO3 samples that were isolated in a

vacuum filtration, dried in a lab oven, and weighed in a digital balance. The table

also shows the average mass of the precipitate for each different water sample

and their standard deviations.

After drying and weighing the precipitate, the percent yield was found.

This showed how accurate the results from the analysis were compared to the

theoretical calculations performed beforehand.

actual yield
Yield of Ca CO3 sample=( ) 100
theoretical yield

Figure 11. Percent Yield of CaCO3

To determine the percent yield of CaCO3 for each sample of water, the

actual yield, which was the mass recorded after drying, was divided by the
 Phillips-Rahman 25

theoretical yield found previously. This result was multiplied by 100 to achieve a

percentage. A sample calculation can be found in Appendix E.

Finally, the water hardness of each sample was calculated using the

average mass of CaCO3.

g Ca CO 3 1000 mg 1000 mL 1
Water hardnessmg/ L of Ca CO3 =
mL 1g 1L 100

Figure 12. Water Hardness

The water hardness for each sample was determined by converting the

average mass of CaCO3 precipitate for the sample in question from g/mL to

mg/L. This result was multiplied by the factor 1/100 to account for the fact that

the sample analyzed was 100 times more concentrated than the original water

sample. A sample calculation can be found in Appendix F.

Table 5
Percent Yield of CaCO3 and Water Hardness
Hard Water Sample Percent Yield (%) Water Hardness (mg/L)

Distilled Water 96.860 431.31

Lake Water 91.010 401.17

Well Water 87.510 382.54

River Water 109.96 477.28

Pool Water 94.300 413.21

Table 5 shows the percent yield of each sample which was found using

the theoretical and actual yields of CaCO 3. The water hardness, which was found

using the average mass of the precipitate, is also shown.

Table 6
Observations
 Phillips-Rahman 26

Hard
Trial
Water
Number Date Observations
Sample

- Tear in the filter paper

- Precipitate poured through the
hole
- Solution seeped around filter
paper and dripped into the flask below
Distilled
1 10/26/16 - Solution was sticky in the drying
Water
oven
- Some precipitate smeared on the
watch glass
- Mass re-recorded 10/27/2016
when precipitate was completely dry

- Solution seeped around filter

paper and dripped into the flask below
- Precipitate was watery
Well
2 10/26/16 - Solution was sticky in the drying
Water
oven
- Mass re-recorded 10/27/2016
when precipitate was completely dry

- Tear in the filter paper

- The precipitate that seeped into
Well the flask by bypassing the filter paper
3 10/27/16
Water was poured back over the filter paper
- Difficulty removing filter paper
from the funnel

- Took longer than usual to

precipitate
- The precipitate that seeped into
the flask by bypassing the filter paper
River
4 10/28/16 was poured back over the filter paper
Water
- Difficulty removing filter paper
from the funnel
- Left to dry over the weekend
(until 10/31/2016)

- The filter paper had to be tapped

River with the stirring rod during filtration
5 10/28/16
Water - Left to dry over the weekend
(until 10/31/2016)
 Phillips-Rahman 27

Hard
Trial
Water
Number Date Observations
Sample

- Precipitate was very thick

- Precipitate was watery even after
Lake filtration
6 10/28/16
Water - Dried in oven for 25 minutes
- Left to dry over the weekend
(until 10/31/2016)

- Took longer than usual to

precipitate
- Wet precipitate was watery
Pool
7 10/28/16 - Solution seeped around filter
Water
paper and dripped into the flask below
- Dried in oven for 14 minutes
- Left over the weekend to dry

- Excess sodium carbonate was

added into the solution after filtration
Distilled
8 10/31/16 already started
Water
- Mass was still slowly decreasing
after a day of drying

- Sodium carbonate took longer

than usual to dissolve in the distilled
water
- Solution seeped around filter
paper and dripped into the flask below
- The precipitate that seeped into
Pool
9 10/31/16 the flask by bypassing the filter paper
Water
was poured back over the filter paper
- Some precipitate smudged onto
the oven mitt when the watch glass was
removed from the drying oven
- Mass was still slowly decreasing
after a day of drying

- Solution seeped around filter

paper and dripped into the flask below
- The precipitate was watery when
Well
10 11/01/16 it came out of the oven
Water
- Some precipitate smudged onto
the oven mitt when the watch glass was
removed from the drying oven
 Phillips-Rahman 28

Hard
Trial
Water
Number Date Observations
Sample

- Filter paper was still moist when

River picked up the day after (11/02/16)
11 11/01/16
Water - Mass re-recorded 11/03/16 when
precipitate was completely dry

- The filter paper flipped over when

Distilled being removed from the funnel
12 11/02/16
Water - Mass was slowly decreasing the
next day

- Solution seeped around filter

Lake paper and dripped into the flask below
13 11/02/16
Water - Mass was slowly decreasing the
next day

- Took a long time for the solution

Pool to precipitate
14 11/03/16
Water - More precipitate than usual went
outside filter paper and made into flask

Lake - Anhydrous sodium carbonate

15 11/03/16
Water stuck to the weighing dish

Table 6 displays the observations made during data collection.

 Phillips-Rahman 29

Figure 13. Initial Precipitate

Figure 13 shows the precipitate formed after mixing the prepared CaCl 2

solution and Na2CO3 solution for about fifteen seconds.

Figure 14. Well-Mixed Precipitate

Figure 14 displays the mixture of the prepared CaCl 2 and the Na2CO3

solutions after it had been mixed for approximately thirty seconds. The substance

resembled milk rather than snow at this point. This is the time when the solution

would start to be filtered through the vacuum filtration apparatus.

 Phillips-Rahman 30

Figure 15. Precipitate During Filtration

Figure 15 is an image of the mixture after excess Na 2CO3 solution was

added and the solution started to filter. When the water was vacuumed out of the

precipitate, the substance that remained looked silky.

Figure 16. Filtered Precipitate

Figure 16 shows the precipitate after it had been filtered through the

vacuum filtration setup. This picture was from when the sample was first placed

into the drying oven and not dried yet. The wet precipitate was smeared onto the

watch glass around the filter paper due to how watery the sample was; however,
 Phillips-Rahman 31

the smeared precipitate was still accounted for in the mass used for the percent

yield. This particular sample looked smooth after it had been filtered.

Figure 17. Dried Precipitate

Figure 17 displays a precipitate dried in the oven for fifteen minutes for

one of the trials. The precipitate was smeared on the watch glass for the sample,

similar to Figure 16. The peaks are due to the precipitate being somewhat sticky

after drying and having been poked with the glass stirring rod.

Data Analysis and Interpretation

 Phillips-Rahman 32

In this experiment, careful measures were taken to assure reliable data

was collected for the mass of each sample so that the final calculated water

hardnesses were accurate. Quantitative data, the mass of the precipitate, was

collected by weighing the precipitate in a digital balance. The first measure taken

was ensuring that all the trials were performed in the same manner, under the

same general conditions, and exposed to the same testing environment. Before

each trial, all materials were cleaned and rinsed with distilled water thoroughly to

remove any remaining precipitate from the previous trial. Each precipitated

sample was dried at approximately 100C for fifteen minutes. Five different types

of water were tested. Samples of distilled water that were made into hard water

by diluting them with a certain amount of CaCl 2 stock solution were the control

group in this experiment. Having a control group was necessary so comparisons

between the other four samples of water that were taken from natural sources

could be made. It helped in determining how hard natural sources of water were

before adding CaCl2 to it and forming a precipitate. Additionally, a control group

helped reduce any confounding due to lurking variables, like other minerals in the

samples of water taken from natural sources. Three separate graduated

cylinders were utilized when preparing solutions that needed CaCl 2, Na2CO3, and

distilled water. This ensured that none of the solutions mixed with one another in

the same graduated cylinder when being measured out, reducing error. Both

CaCl2 anhydrous and Na2CO3 anhydrous were weighed in their own dishes and

dissolved in their own beakers prior to forming the precipitate. For each trial, a

new piece of filter paper was used. In addition, the trials were randomized to
 Phillips-Rahman 33

avoid potential error with testing and equipment. A randomizing function on TI-

Nspire software determined the molarity for each of the five types of water and

the order of the fifteen trials. This helped reduce any possible bias that may have

occurred which would have resulted in inaccurate data. Lastly, the trials were

repeated to ensure consistency. Three trials were run independently for each of

the five types of water in order to reduce variability and possible errors in the

data and final results.

To analyze the normality of the data, normal probability plots were created

for the water hardnesses of the five different water types.

Figure 18. Distilled Water Samples Probability Plot

Figure 18 shows the normal probability plot for the water hardnesses of

the precipitated samples from distilled water. This plot displays that the distilled

water samples have a fairly normal distribution and seem to follow a fairly linear

pattern. No extreme skewness is visible. There appears to be one outlier but it is

not extreme. The moderately steep slope of the line shows that there was not

much variability in the water hardnesses of the distilled water samples.

 Phillips-Rahman 34

Figure 19. Lake Water Samples Probability Plot

Figure 19 shows the normal probability plot for the water hardnesses of

the precipitated samples from lake water. This plot displays that the lake water

samples have a normal distribution and seem to approach a linear pattern. No

extreme skewness is visible. There appears to be one outlier but it is not

extreme. The extremely steep slope of the line proves that there is little variability

between the water hardnesses of the lake water trials.

 Phillips-Rahman 35

Figure 20. Well Water Samples Probability Plot

Figure 20 shows the normal probability plot for the water hardnesses of

the precipitated samples from well water. This plot displays that the well water

samples have a somewhat normal distribution and seem to approach a linear

pattern. No extreme skewness is visible. There appears to be one outlier but it is

not extreme. The shallow slope of the line means that there was quite a bit of

variability in the water hardnesses of the well water trials.

 Phillips-Rahman 36

Figure 21. River Water Samples Probability Plot

Figure 21 pictures the normal probability plot for the water hardnesses of

the precipitated samples from river water. This plot portrays that the river water

samples have a roughly normal distribution and seem to approach a linear

pattern. No extreme skewness is visible. There appears to be one outlier but it is

not extreme. The slope of the line is not very steep which is due to the large

variability between the water hardnesses of the river water trials.

 Phillips-Rahman 37

Figure 22. Pool Water Samples Probability Plot

Figure 22 shows the normal probability plot for the water hardnesses of

the precipitated samples from pool water. This plot shows that the pool water

samples have a normal distribution and seem to approach a linear pattern. No

extreme skewness is visible. There appears to be one outlier but it is not

extreme. The slope of the line is remarkably steep; there was hardly any

variability among the water hardnesses of the pool water samples.

Furthermore, the normal probability plots show that the data collected in

the experiment was fairly accurate and is a good representation of the calculated

water hardnesses. The data appears to be relatively normal, and a one-sample t

confidence interval can be calculated to obtain the interval that tries to estimate

the true population mean for each type of water.

For this data, the statistical treatment that was the most appropriate to use

was a one-sample t confidence interval because the true population mean, or

average water hardness, for each of the five types of water was not known, but

an interval was able to be found that captured the mean. To correctly calculate a
 Phillips-Rahman 38

one-sample t confidence interval, two conditions were required. The first

condition was met, which was having independent simple random samples for

the given number of populations in this experiment, five. Since the normal

probability plots depicted a fairly normal distribution for the data overall, the

second condition was also met. In addition, the rule of thumb was satisfied as

show below:

N >10 n

Figure 23. Rule of Thumb

In the figure above, N is the population of different types of water in the

universe, and n is the number of data points in this experiment, which even

multiplied by ten is still much less than the overall population. More detailed

procedures and a sample calculation for a one-sample t confidence interval can

be found in Appendix H.
 Phillips-Rahman 39

Figure 24. Distilled Water Confidence Interval

Figure 24 above shows the results of calculating the one-sample t

confidence interval for the distilled water samples. It can be concluded that 95%

of the samples give an interval from approximately 122.51 to 740.11 milligrams of

CaCO3 per liter that will capture the true mean population of water hardness for

distilled water.

Figure 25. Lake Water Confidence Interval

Figure 25 above shows the results of calculating the one-sample t

confidence interval for the lake water samples. It can be concluded that 95% of
 Phillips-Rahman 40

the samples give an interval from approximately 368.13 to 434.22 milligrams of

CaCO3 per liter that will capture the true mean population of water hardness for

lake water.

Figure 26. Well Water Confidence Interval

Figure 26 above shows the results of calculating the one-sample t

confidence interval for the well water samples. It can be concluded that 95% of

the samples give an interval from approximately 0 to 1031.7 milligrams of CaCO 3

per liter that will capture the true mean population of water hardness for well

water. Although the lower bound of the interval was a negative value, it was

changed to 0 in the stated interval because negative water hardness values do

not exist.
 Phillips-Rahman 41

Figure 27. River Water Confidence Interval

Figure 27 above shows the results of calculating the one-sample t

confidence interval for the river water samples. It can be concluded that 95% of

the samples give an interval from approximately 0 to 1267.0 milligrams of CaCO 3

per liter that will capture the true mean population of water hardness for river

water. Although the lower bound of the interval was a negative value, it was

changed to 0 in the stated interval because negative water hardness values do

not exist.
 Phillips-Rahman 42

Figure 28. Pool Water Confidence Interval

Figure 28 above shows the results of calculating the one-sample t

confidence interval for the pool water samples. It can be concluded that 95% of

the samples give an interval from approximately 388.40 to 438.02 milligrams of

CaCO3 per liter that will capture the true mean population of water hardness for

pool water.

After calculating confidence intervals for each of the five populations of

water and looking at the normal probability plots, it can be concluded that the

data was distributed normally, and the experiment was carried out correctly with

accurate results. The confidence intervals for well water and river water

contained zero and slightly larger numbers than expected possibly because of

errors made during experimentation. One trial for each of those water types had

a much higher mass than the theoretical amount, which would have also

increased the water hardness for each. However, the rest of the data can be

deemed reliable and correct. Moreover, the data analysis and interpretations
 Phillips-Rahman 43

provided support to reject the experiments hypothesis that gravimetric analysis is

not accurate in evaluating water hardness.

Conclusion
 Phillips-Rahman 44

In this experiment, gravimetric analysis was utilized to determine water

hardness in the form of CaCO3 on five types of water samples. After completing

the trials, the masses of the precipitated samples were converted to water

hardnesses, and the percent yield for each type of water was found using the

actual mass obtained from the experiment and theoretical mass calculated

beforehand. The final results obtained from this experiment and the statistical

treatments specifically the high percentage yields and reasonable one-sample t

confidence intervals led to the rejection of the hypothesis and conclusion that

gravimetric analysis is reliable when determining the hardness of water.

However, it is a time-consuming and tedious process with much room for error if

precaution is not taken.

These results can be clarified by scientific concepts that were previously

explained. It was stated that in order for gravimetric analysis to be correct, certain

conditions had to be satisfied, such as the ion being analyzed must have been

completely precipitated, the precipitate must have been a pure compound, and

the precipitate had to be easily filtered (Wired Chemist). In this experiment, the

precipitate formed was CaCO3, and the ion being analyzed was Ca2+. Calcium

carbonate is considered virtually insoluble in water and is thus an ideal candidate

for the gravimetric determination of Ca2+ ions. It has a stable condition but exists

as a potential hexahydrate. Heating the precipitate to approximately 100C

ensured that the solid was thoroughly dried to remove the waters of hydration so

the percent yield determination was accurate. The high percent yield data from

the experiment support this statement. From the data, it was seen that the
 Phillips-Rahman 45

percent yields for each type of water were the following: distilled water, 96.860%;

lake water, 91.010%; well water, 87.510%; river water, 109.960%; and pool

water, 94.300%. Besides river water, the percent yields turned out reasonably

high. Slowly adding the precipitating agent in gravimetric analysis ensured even

mixing and helped prevent supersaturation, which would have led to small

particles or even a colloidal solution. Within this experiment, precipitation of

excess Na2CO3 relieved supersaturation. To increase the particle size of a

precipitate so it was not easily filterable, the relative supersaturation during the

precipitate formation was minimized. Digestion, or heating and then cooling the

mixture, essentially promoted recrystallization of the solid, which lead to larger

crystal or particle growth and also helped remove impurities that might have been

adsorbed on the surface (Texas A&M University). For each type of water sample,

these were the following theoretical hardnesses compared to the average

hardnesses obtained from the experimental results in milligrams of CaCO 3 per

liter: distilled, 445:431.31; lake, 441:401.17; well, 437:382.54; river, 434:477.28;

and pool, 438:413.21. Therefore, it can be concluded that gravimetric analysis is

an accurate technique for the determination of CaCO 3 in hard water, as long as

the necessary measures to ensure accuracy are taken.

The results of this experiment agree with previous experiments and work

done in this field. For instance, researchers Jarryd Campbell and Dan Peterson

from Concordia College conducted an experiment in 2010 where the hardness of

water was determined using flame atomic absorbance spectrometry, an

alternative method to common and traditional titration methods. Their research

 Phillips-Rahman 46

found that their hypothesis was indeed correct: river water was much harder

compared to tap water and water from drinking fountains. In this experiment, river

water was found to have a higher percent yield than the rest of the samples, and

happened to be the only one over 100% at 109.96%; the average water

hardness was higher than the rest, being the only nearing 500 at 477.28

milligrams of CaCO3 per liter; and the one-sample t confidence interval contained

extremely large numbers, at 0 to 1267.0 milligrams of CaCO 3 per liter. Other

minerals in the river water such as K+, Mg+, Na+, and P-3, to name a few could

have produced these results (Ocean and River Chemistry). Furthermore, the

results obtained in this experiment concurred with other final results of previous

experiments as well, validating that this experiment was conducted successfully.

Certain steps could have been taken to ensure more accuracy in the final

results. One significant issue was the size of the filter paper. The only filter paper

available to fit the Bchner funnel was 5.5 centimeters in diameter, and this was

just large enough to cover the holes of the funnel. This size filter paper became a

problem because it would allow the solution being filtered to seep into the flask

rather than sit atop of the filter paper like it was supposed to. Because time was

limited, this lost precipitate could not be repoured over the filter paper and

accounted for. Regardless, repouring the precipitate that made it into the flask

was difficult because it mixed with the water already filtered into the flask.

Filtering this watery precipitate again proved to be very tedious, as it would easily

evade the filter paper and seep back into the flask. The precipitates from trial 2,

6, and 11 were recorded as watery, and the masses of those precipitates were
 Phillips-Rahman 47

higher compared to the non-watery ones. For instance, the masses of the

precipitates from the first two trials for the well samples were as follows: 1.3993

and 1.1551 grams, respectively. However, in the third well trial in which the

watery precipitate had to be filtered again, the final mass turned out to be

approximately 3.7575 grams.

This study, which was carried out in a manner different than that of other

experiments, provided more evidence for the scientific community to support the

hypothesis that gravimetric analysis is an efficient method to evaluate water

hardness. Future research could use the results from this experiment to study

whether other factors such as age of water sample, temperature of drying oven,

or pressure of vacuum filtration apparatus, combined with concentration of

solution affects the accuracy of gravimetric analysis. For example, variables such

as the amount of other minerals in samples of water from natural sources, could

be measured along with water hardness. These other minerals could be removed

from the water through precipitation formation as well and then quantified. Data

collected in such a way would help expand this field of study by providing further

information on the properties of water and how to treat it. While this hypothesis

and method of experimentation were both similar to other experiments, this

research was performed in a more precise fashion, providing authentic results.

The outcome of this research showed that the hardness of any type of water,

such as salt water from the ocean or even bottled water, can also be calculated.

In addition, the formation of other precipitates and their effect on the

 Phillips-Rahman 48

determination of water hardness can be explored, for it is known that there are

other ions that contribute to water hardness besides Ca 2+.

Conclusively, this researchs experimental process and results can be

used in municipal water plants. By filtering water with vacuum filtration and

calculating its hardness, municipal water plants will be able to decide on the

quantity of the solutions needed to treat the water and make it potable. They will

be able to use this method to determine water hardness because the hypothesis

was rejected and gravimetric analysis was deemed accurate. Therefore, this

crucial branch of research proves to be beneficial to the development of

humanity itself as it facilitates the betterment of lifes most mandatory ingredient:

water.

Acknowledgements

Special thanks go out to all MMSTC teachers for aiding in the research.

Mrs. Hilliard helped by supplying various materials to use, such as the

gravimetric analysis lab kit from Flinn, vacuum filtration apparatus, a drying oven,
 Phillips-Rahman 49

and a digital balance. Without all these lab materials and the actual lab to

conduct the experiment in, this research would not have been feasible.

Mrs. Tallman made sure all of the collected data was easily portrayed and made

understandable. Mrs. Cybulski aided by helping to determine which method of

statistical analysis should be used, as well as giving insight on whether the

analysis was calculated correctly. Much appreciation goes to one of the lab

managers from the Port Huron Wastewater Treatment Plant, Patricia Troy, who

helped in explaining what kind of softening techniques modern municipal plants

utilize. Lastly, all of the parents must be thanked for their provision of support.

Much of this research would not have been possible without these contributors.

Appendix A: Vacuum Filtration Apparatus

 Phillips-Rahman 50

Figure 29. Vacuum Filtration Setup (Suction Filtration)

Figure 29 above shows the general setup of a vacuum filtration. The

materials needed to create the setup include a 500 mL Erlenmeyer flask, a

Bchner funnel, a rubber adapter, latex rubber tubing, a ring stand and ring

clamp, and a vacuum aspirator. One end of the latex rubber tubing is connected

to the vacuum aspirator which is attached to the faucet and the other end is

connected to the Erlenmeyer flask. The Erlenmeyer flask is attached to a ring

stand with a clamp to ensure the force of the suction does not tip it over. A piece

of filter paper is placed in the Bchner funnel, which is attached to a rubber

adapter and inserted firmly into the flask.

Appendix B: Hard Water Collection

Table 7
 Phillips-Rahman 51

Hard Water Collection

Date Time Location Sample Quantity

Detroit River at Belle

10/09/2016 11:00 AM River Water 1L
Isle in Detroit, MI

Warren Mott High

10/10/2016 5:30 PM School swimming pool Pool Water 1L
in Warren, MI

Canal in Saint Clair

10/22/2016 2:30 PM Lake Water 1L
Shores, MI

House Spigot in Lake

10/22/2016 4:00 PM Well Water 1L
Orion, MI

The table above displays the specific details of when and where the hard

water samples were collected, excluding distilled water because it was bought at

a store and not manually collected.

Appendix C: Solution Preparation

Table 8
Solution Preparation
 Phillips-Rahman 52

Sample Concentration Preparation

V
( 1)=( 0.100 M )(100 mL)
Distilled Water 0.100 M
(2 M )
V 1=5 mL

V
( 1)=( 0.200 M )(100 mL)
Lake Water 0.200 M
(2 M )
V 1=10 mL

V
( 1)=( 0.300 M )(100 mL)
Well Water 0.300 M
(2 M )
V 1=15 mL

V
( 1)=( 0.400 M )(100 mL)
River Water 0.400 M
(2 M )
V 1=20 mL

V
( 1)=( 0.500 M )(100 mL)
Pool Water 0.500 M
(2 M )
V 1=25 mL

Table 8 above lists the five different water samples and their assigned

concentrations. The calculations to determine how much stock CaCl 2 solution is

needed to be diluted to prepare 100 mL of each sample are shown as well. To

find how much CaCl2 stock solution is needed, the dilution formula is needed.

M 1V 1 M 2V 2

Figure 30. Dilution Formula

In the formula above, M1 and V1 represent the molarity and volume of the

sample before, and M2 and V2 represent the molarity and volume of the sample

after the dilution. It is known that 2 M CaCl2 stock solution is being used before
 Phillips-Rahman 53

the dilution, and a specified molarity (according to the trial) and 100 mL of

solution need to be achieved after. Using this information, V1, the volume of

CaCl2 stock solution needed for dilution, was found.

Appendix D: Moles of Ca2+ and Excess Na2CO3 Calculations

Moles of Ca2+ in 20 mL of prepared solution:

mol
M=
L
 Phillips-Rahman 54

2+
Ca
mol
0.020 L
0.100 M =
2+=0.100 M 0.020 L

mol Ca
2+
0.002 mol Ca

Moles of Ca2+ in 2.0 g of anhydrous:

Ca+2Cl CaCl 2
2+
2+
Ca
1 mol =0.018022 mol Ca
1 mol CaCl 2
1mol Ca Cl2
2.0 g Ca Cl2
110.978 g Ca Cl2

Figure 31. Sample Calculations for Moles of Ca 2+

The sample calculations above were performed in order to find the amount

of moles in 20 mL of prepared solution and 2.0 g of CaCl 2 anhydrous for each

water sample. In the first formula, M represents the molarity to be achieved for

each water sample. The amount of Ca2+ ions in moles, which is represented by

mol, is divided by the volume of the solution, L. Next, the 2.0 g of anhydrous is

converted to moles of Ca2+ by dividing grams of CaCl2 present per mole of CaCl2

and multiplying that result by moles of Ca 2+ per mole of CaCl2. To find the total

amount of moles, moles of solution and moles of anhydrous were added.

1L
1 mol Ca2 + 1.2
0.5 mol Na2 CO 3
1 mol Na2 CO3
2+
Vof Na2 CO3 =0.002 mol Ca

0.0048 L=4.8 mL 5 mL
 Phillips-Rahman 55

Figure 32. Sample Calculation for Excess Na2CO3

The sample calculation above was completed in order to determine the

amount of excess Na2CO3 solution needed to ensure that all the Ca 2+ ions in

solution were converted to product. First, the number of moles of Ca 2+ in 20 mL of

the CaCl2 solution was found. This was used in determining how many Ca 2+ ions

reacted with 1 mole of Na2CO3 which had a molarity of 0.5 M. Finally, the result

was multiplied by 1.2 to provide a 20% excess.

Appendix E: Percent Yield Calculations

Percent Yield of CaCO3 in sample:

actual yield
( ) 100
theoretical yield
1.9409 g
( ) 100
2.00388 g
96.86
 Phillips-Rahman 56

Figure 33. Sample Calculation for Percent Yield of CaCO 3

The sample calculation above was completed in order to determine the

percent yield of CaCO3 in a hard water sample. To determine it, the actual yield,

which was the mass recorded after drying, was divided by the theoretical yield

found previously. This result was multiplied by 100 to get a percentage.

Appendix F: Water Hardness Calculations

Water hardness in mg/L of CaCO3:

2.00388 g CaCO 3 1000 mg 1000 mL 1

45 mL 1g 1L 100

445.301 mgCa CO3 / L( ppm)

Figure 34. Sample Calculation for Water Hardness

Figure 34 above shows the sample calculation that was completed to

determine the hardness of water for each sample. The mass of the dried
 Phillips-Rahman 57

precipitate was converted to mg/L and multiplied by the factor 1/100 to account

for the fact that the sample analyzed was 100 times more concentrated than the

original water sample.

Appendix G: Theoretical Amount of CaCO3 Precipitate Calculations

Theoretical Amount of CaCO3:

100.086 g Ca CO3
2+ =2.00388 g CaCO 3
1 mol CaCO 3
0.02002 mol Ca

Figure 35. Sample Calculation for Theoretical Amount of CaCO 3 Precipitate

In the equation above, the sum of the moles present in 20 mL of prepared

solution and 2.0 g of CaCl2 anhydrous was multiplied by the theoretical mass of

CaCO3 present per mole of CaCO3. This result was interpreted as the theoretical

amount of CaCO3 precipitate to be formed by a water sample.

 Phillips-Rahman 58

Appendix H: One-Sample t Confidence Interval

The statistical analysis method used in this experiment was a one-sample

t confidence interval. All the statistics and sample calculations are shown below.

Table 8
One-Sample t Confidence Interval Statistics
Hard Water nx sx
x
Sample

Distilled Water 3 431.31 124.31

Lake Water 3 401.17 13.302

Well Water 3 382.54 261.31

River Water 3 477.28 317.91

Pool Water 3 413.21 9.9877

 Phillips-Rahman 59

Table 8 above shows the statistics for the one-sample t confidence

interval. The sample sizes, sample means, and sample standard deviations are

provided.

The formula needed in order to calculate this interval is shown below.

sx

x t

Figure 35. One-Sample t Confidence Interval Formula

For this formula, the means, standard deviations, and sample sizes of

each individual population must be known. In the formula, xxstands for the

sample mean, sx stands for the sample standard deviation, and nx stands for the

sample size. The confidence level is represented by t * also called the upper

critical value and df means degrees of freedom, used to find confidence levels.

sx

x t
124.31

431.31 4.303
122.51,740.11

Figure 36. Sample Calculation for One-Sample t Confidence Interval

Figure 36 shows a sample calculation to find a one-sample t confidence

interval. It can be concluded that 95% of the samples give an interval from

approximately 122.51 to 740.11 milligrams of CaCO 3 per liter that will contain the

true mean population mean of water hardness for distilled water.

 Phillips-Rahman 60

Works Cited

Braff, Daniel. Hard facts about tap water. Chicago Tribune. N.p., 25 April 2012.

Web. 27 Nov. 2016. <http://articles.chicagotribune.com/2012-04-25/health/

sc-health-0425-hard-soft-water-20120425_1_hard-water-soft-water-

calcium-and-magnesium>.

Campbell, Jarryd and Dan Peterson. Determination of water hardness from

common water sources using flame atomic absorbance spectrometry.

Concordia College, 2010. Web. 20 Sept. 2016.

<http://dept.cord.edu/chemistry/CCJAC/2010_Vol_1/2010_1_4.pdf>.

Casiday, Rachel and Regina Frey. Water Hardness. Washington University, n.d.

Web. 20 Sept. 2016. <http://www.chemistry.wustl.edu/~edudev/

LabTutorials/Water/FreshWater/hardness.html>.
 Phillips-Rahman 61

"CHAPTER XV: GRAVIMETRIC METHODS." University of Massachusetts

Amherst, n.d. Web. 20 Sept. 2016. <http://www.ecs.umass.edu/cee/

reckhow/courses/572/572bk15/572BK15.html>.

Fisherman, Marvin J. and Linda C. Friedman. Methods for Determination of

Inorganic Substances in Water and Fluvial Sediments. USGS

1989: 466.

Texas Water Resources Institute. Web. 20 Sept. 2016.

<http://pubs.usgs.gov/twri/twri5-a1/pdf/TWRI_5-A1.pdf>.

Gravimetric Analysis of Calcium and Hard Water. Flinn Scientific, Inc., 2013.

Web. 15 Sept. 2016.

"Gravimetric Analysis." Texas A&M University, n.d. Web. 20 Sept. 2016.

<https://www.chem.tamu.edu/class/majors/tutorialnotefiles/

gravimetric.htm>.

Gravimetric Analysis. Wired Chemist. N.p., n.d. Web. 20 Sept. 2016.

<http://www.wiredchemist.com/chemistry/instructional/laboratory-tutorials/

gravimetric-analysis>.

Leurs, Lina J., et al. "Relationship between Tap Water Hardness, Magnesium,

and Calcium Concentration and Mortality Due to Ischemic Disease or

Stroke in the Netherlands." Environmental Health Perspectives 118

(2010): n. pag. Questia. Web. 20 Sept. 2016. <https://www.questia.com/

article/1G1-222476946/

Relationship-between-tap-water-hardness-magnesium>.
 Phillips-Rahman 62

Mesquita, Rielis. Hard Water And Your Home. Aqualiteus. N.p., 10 Feb. 2014.

Web. 26 Nov. 2016. <http://www.aqualiteus.com/blog/

hard-water-problems-and-your-home>.

"Ocean and River Chemistry." Department of Earth & Environmental Sciences.

Columbia University, n.d. Web. 20 Nov. 2016 <http://eesc.columbia.edu/

courses/ees/lithosphere/hays_tutorial_3/ hydro.htm>.

Perlman, Howard. "Water Hardness." USGS Science for a Changing World. The

USGS Water Science School, 2 May 2016. Web. 20 Sept. 2016.

<http://water.usgs.gov/edu/hardness.html>.

Suction Filtration. Digital image. York University, n.d. Web. 21 Oct. 2016.

<http://www.chem.yorku.ca/profs/hempsted/chemed/equipment/

suction.html>.

Troy, Patricia. "Re: Student Research Assistance." Message to Megan Phillips.

05 Oct. 2016. E-mail.

Wisler, C.O., G.J. Stramel, and L.B. Laird. Water Resources of the Detroit Area

Michigan (n.d.): n. pag. United States Geological Survey. Web. 2

Oct. 2016. <http://pubs.usgs.gov/circ/1952/0183/report.pdf>.