W

Activity 3: Quantifying Solutes Experimentally finding concentrations

Now that you have a basic understanding of what is soluble in water and why a substance is soluble in water, it is time to learn to quantify how much solute is present in various water samples. Through this activity you will learn three methods for calculating the concentration of various solutes within a natural water sample: titrations, colorimetry, and probeware.

P R E P A R I N G WHAT DO YOU THINK? LEARNING OBJECTIVES

Your instructor will demonstrate using a conductivity probe to determine a reading called Total Dissolved Solids for a few various samples including distilled water and your water sample(s). Generally, what type of dissolved solids do you think a conductivity probe measures? Explain. Specifically, what dissolved solids do you think are present in your specific sample? Why?

Record your ideas in your chemistry notebook. Be prepared to discuss your responses with your small group and the class. Finally, include the objective or essential question for this activity.

E X P E R I M E N T I N G TITRATION COLORIMETRY PROBEWARE

Part A: Titration for Water Hardness

Around Culver, everyone has heard of soap scum found around bathtubs or in the shower? That soap scum is a result of hard water forming insoluble precipitates with soap molecules. Water is described as 2+ 2+ hard when it contains a high concentration of Mg and Ca ions 9 (150 ppm or greater). The concentration of these ions may be found by adding another solution, EDTA (ethylenediaminetetraacetic 2+ 2+ acid) that can remove the Mg and Ca ions completely from the water sample. To determine the concentration of the ions causing the hardness, you must know the molar concentration of the EDTA and exactly how much of it must be added to remove all of the ions. If you know these two quantities and the reaction (below), then you can use the stoichiometry you learned in previous chapters to solve for the 2+ concentration of the hard ions, symbolically represented by M . M
2+ (aq)

+ EDTA(aq) M - EDTA(aq)
Before Titration M2+ +EBT Endpoint

2+

The water hardness may be found by titrating a water sample with a 0.010M solution of EDTA, which as the equation 2+ 2+ symbolizes, forms a soluble complex with the Mg and Ca ions, effectively removing them as free ions in solution. The 2+ 2+ titration is complete when all of the Mg and Ca ions have been bound to EDTA molecules. Both the soluble ions and EDTA are clear in solution, though, so you must find a way to visualize this point at the macroscopic level. To do this you will

M2+ -

EBT

add a small amount of an indicator dye called EBT (Eriochrome Black T), which binds to a small fraction 2+ 2+ 2+ 2+ of the Mg and Ca ions. As long as all the indicator dye is bound to the Mg and Ca ions, the solution will be wine red. Once the EDTA has bound to all the free metal ions, it will replace the indicator dye. The free dye will turn the solution blue illustrating the end of the titration. 1. Copy the table below into your chemistry notebook. Table 1: Titration Data
Initial Volume of EDTA (mL) Final Volume of EDTA (mL) Volume of EDTA Titrated (L) Moles of EDTA Titrated (mol) Moles of 2+ Ca in the Water Sample (mol) Volume of Water Sample (L) Concentration of 2+ Ca in the Water Sample (M)

Trial

Concentration of EDTA (M)

Trial 1 Trial 2

0.00500 0.00500

0.040 0.040

2. Prepare the set up demonstrated by your instructor. 3. Fill the buret with 0.00500 M EDTA solution. Record the initial volume reading on the buret in the table in your chemistry notebook. 4. In the 150 mL Erlenmeyer flask add 40.0 mL of a water sample, 10.0mL of pH 10 buffer and around 30 drops of EBT indicator. The solution in the Erlenmeyer flask should be wine red like figure 3.1a. We may add more or less EBT after taking a look at our initial results. 5. Slowly add the 0.00500 M solution of EDTA in the buret to the EBT-M solution in the Erlenmeyer flask. Swirl the solution as you add the EDTA solution. When the color flashes blue in the Erlenmeyer flask, add the EDTA drop by drop until the solution in the Erlenmeyer flask stays blue. The color blue indicates the end point of the titration has been reached and EDTA 2+ 2+ has formed a complex with all of the Mg and Ca ions in solution. 6. Record the final volume of EDTA in the table in your chemistry notebook. 7. Calculate and record the volume of the EDTA solution titrated into the water sample. Convert this number from mL to L, recalling that 1.0000L = 1000.0mL. Record this value in your chemistry notebook. 8. Complete the first row of the table by performing the necessary stoichiometric calculations and conversions. A sample problem can be found in the Analyzing section for this lab. a. The moles of EDTA are found by multiplying the solution concentration (0.00500M) times the volume (L) that had to be added to reach the endpoint. b. From the equations it can be determined that one EDTA molecule combines with one Mg or 2+ 2+ 2+ Ca ion; therefore the moles of EDTA added equals the total moles of Mg and Ca in the water sample when the titration is complete. c. The unknown concentration of the Mg and Ca ions (M) is equal to the total moles of M ions divided by the volume of the water sample (0.040L).
2+ 2+ 2+ 2+ 2+

d. This is a weird step. Water scientists measure water hardness in ppm of calcium carbonate, assuming all of the calcium is from calcium carbonate in the bedrock of the aquifer. To determine water hardness in ppm (mg/L), you use the molar mass of calcium carbonate to convert the moles of calcium (from calcium carbonate) to grams of calcium carbonate to milligrams of calcium carbonate. Divide this by the volume in L to determine ppm. 9. Repeat steps 3 8 for a second 40.0mL sample of you water, making sure you have cleaned and rinsed the Erlenmeyer flask well. If your instructor directs you to do so, you may also have a third sample of water to titrate.

Part B: Colorimetry
Iron is commonly found in water supplies as it is one of the most abundant substances in the Earth, making up nearly 5% of the Earths crust. Some igneous rocks contain iron in a variety of forms like ferromagnesian minerals, mica, iron(II) sulfide (FeS), iron pyrite (FeS2), hematite (Fe2O3), and magnetite (Fe3O4). Sandstone rocks also contain iron as oxides, carbonates, sulfides and clay minerals. Iron also frequently enters water supplies through pipes and waterways. Although iron can occur in water in two 2+ 3+ 2+ 3+ oxidation states, iron(II) (Fe ) and iron(III) (Fe ), the Fe quickly converts to Fe when the water is exposed to air. Small amounts of iron(III) are safe in water supplies; therefore, iron(III) is considered a secondary contaminate by the EPA. The concentration of iron in a water sample may be determined quantitatively by reacting the Fe ions 2+ with an indicator consisting of thiocyanate ions, SCN , to produce deep-red complex ions, [Fe(SCN)] . 3+ You did this in AC2: Qualitative Analysis. Even very dilute solutions of Fe will show a pink color when the thiocyanate concentration is high. In colorimetry, the varying shades of color can be measured to determine the concentration. A colorimeter, an instrument designed to measure the intensity of color in a solution, will be used to get a more quantitative measure.

3+

You will use a spectrophotometer to measure the concentration of each solution. In this experiment, you will first determine the wavelength of light from the LED light source that will pass through the solution and strike a photocell. Once chosen, you will use the theory that a higher concentration of the colored solution absorbs more light (and transmits less) than a solution of lower concentration. The spectrophotometer monitors the light received by the photocell as percent transmittance.

You will use four iron(III) solutions of known concentration (standard solutions). Each solution is transferred to a small, rectangular cuvette that is placed into the spectrophotometer. The amount of light that penetrates the solution and strikes the photocell is used to compute the absorbance of each solution. When you graph absorbance vs. concentration for the standard solutions, a direct relationship should result. The direct relationship between absorbance and concentration for a solution is known as Beers law. You will determine the concentration of the iron(III) in the water sample by measuring its absorbance with the spectrophotometer. By locating the absorbance of the unknown on the vertical axis of the graph, the corresponding concentration can be found on the horizontal axis. The concentration of the unknown can also be found using the slope of the Beers law curve. 1. Obtain the prepared reference standards with known concentrations of iron(III) (Fe ) of 1.0 ppm, 3.0 ppm, 5.0 ppm and 10.0 ppm. If reference standards have not been prepared for you, then use the dilution formula (M1V1 = M2V2 ) and your volumetric flask to create the solutions as directed by your instructor. 2. Measure 10.0mL of each of the reference standards into 4 flat bottom vials or test tubes. Lightly label the top of each vial with the corresponding concentration. 3. Add 2 drops of 0.10M NH4SCN to each of the reference standards to create [Fe(SCN)] . 4. Use a USB cable to connect a Vernier Spectrometer or a Vernier SpectroVis to a LabQuest. 5. Turn on the LabQuest and choose New from the File menu.
2+ 3+

6. Calibrate the spectrometer. a. Prepare a blank by filling an empty cuvette full with distilled water. b. Tap the reddish-orange meter box and select Calibrate. The following message appears in the Calibrate dialog box: Waiting seconds for lamp to warm up. After the allotted time, the message changes to: Finish Calibration. c. Place the blank in the spectrometer; make sure to align the cuvette so that the clear sides are facing the light source of the spectrometer. Select Finish Calibration. When the message Calibration Completed appears, after several seconds, select OK. 7. Determine the maximum wavelength for [Fe(SCN)] (aq) and set up the data collection mode. a. Empty the blank cuvette and rinse it twice with small amounts of the 10.0 ppm 2+ [Fe(SCN)] solution. 2+ b. Fill the cuvette full with the 10.0 ppm [Fe(SCN)] solution and place it in the spectrometer. 2+ c. Start the data collection. A full spectrum graph of the [Fe(SCN)] solution will be displayed. Tap Stop to complete the analysis. d. Tap on the wavelength of maximum absorbance ( max). Use the left- and right-hand arrow keys to fine tune your trace, if necessary. Go back to the meter screen. Tap the mode box. Change the mode to Events with Entry. e. Enter Concentration for the name and ppm for the units. Select OK to continue. f. The LabQuest will now prompt you to either save or discard the full spectrum data. Discard the data. 8. Collect absorbance-concentration data for the five standard solutions. a. Leave the cuvette in the spectrometer and start the data collection. When the absorbance reading stabilizes, tap Keep. Enter 10.0 as the concentration and select OK. b. Discard the cuvette contents in the waste container at your station. Using the 5.00 ppm solution, rinse and fill the cuvette full. Wipe the cuvette and place it in the spectrometer. When the absorbance reading stabilizes, tap Keep. Enter 5.00 as the concentration. 2+ c. Repeat Step 8b for the remaining vials or test tubes of the standard [Fe(SCN)] solution. When you have finished testing the standard solutions, stop the data collection. 9. To display a graph of absorbance vs. concentration with a linear regression curve: a. Choose Curve Fit from the Analyze menu. b. Select Linear as the Fit Equation. c. Select OK. The graph should indicate a direct relationship between absorbance and concentration, which is Beers law. The regression line should closely fit the five data points and pass through (or near) the origin of the graph. Record the best-fit line equation for the standard solutions in your data table. 10. Determine the concentration of the unknown Fe solution. a. Prepare a 10.0 mL sample of the unknown iron(III) solution with equal drops of the indicator as the rest of your experiment. b. Rinse the cuvette twice with the unknown solution and fill it about full. Wipe the outside of the cuvette and place it into the spectrometer. c. Tap Meter and monitor the absorbance value displayed on the screen. When this value has stabilized, record it in your data table. d. Tap Graph and trace the best-fit line equation to determine the concentration of your 2+ unknown [Fe(SCN)] solution. Use the left- and right-hand arrow keys to fine tune your trace. 11. Dispose of any of the remaining solutions as directed.
3+ 2+

Part C: Ion-specific electrodes (pH)

pH is a very specific measure of concentration. It is a measure that specifically relates to the amount of hydrogen ion in solution. This is often a very small number, so instead of using molarity (M) or parts per million (ppm), people who measure pH use the pH scale that youve been introduced to over your science careers from 1 14. High measures of pH indicate a base, which actually has very little hydrogen ion. Low measures of pH indicate an acid, which actually have very large amounts of hydrogen ion. Why is this backwards you may ask?!?? Well, pH is defined as the log of the hydrogen ion concentration (in Molarity). It is a math function that we used to get simple, positive numbers for the general public from complicated concentrations. Your instructor will share the pH equations and how to use your calculator to determine these numbers and share the relavent formulae to use to convert pH to M of hydrogen ions and M of hydrogen ions to pH. We can use ion-specific electrodes to measure amounts of an ion in solution. They work by having selective membranes, little plastic disks with special pours, specific to the ion the electrode is designed to measure. They can be found for a number of ions, including those commonly present in natural waters including hydrogen ion (pH), chloride, ammonium, calcium, phosphate, and nitrate. 1. Prepare the nitrate probe according to the probes specific directions. This often involves soaking the probe in a concentrated solution for an hour before class. Calibrate the probe according to the probes specific directions. Your instructor will let you know if this step has been done for you prior to class. 2. Take the reading for your water sample. a. Pour 100mL of your water sample into a clean beaker. b. Rinse the probe with distilled water and carefully blot it dry. c. Insert your probe into the water sample and gently swirl for a few seconds. d. When the reading stabilizes, record the value from the ion-specific probe in your chemistry notebook. 3. Calculate the concentration of hydrogen ion, [H+], in each solution. Note that [H+] = 10 Record these molar concentration values in the table in your chemistry notebook.
-pH

A N A L Y Z I N G READING WHAT DO YOU THINK NOW? QUESTIONS

Reading: Quantifying Solutes

Getting Analytical
Analytical chemistry has two broad goals: identifying what chemicals are present and measuring the amounts of the chemicals. In Activities 1 and 2, you learned ways in which you can identify and predict what chemical solutes are present in the water. In this activity, you learned three techniques to analyze the amounts of chemical solutes in natural water supplies: titration, colorimetry, and ion-specific probes. Amounts of substances in solution are often compared using molar concentrations. A solution with a concentration of 1.0 molar (or 1.0M) has 1.0 mole of structural units dissolved in each liter of the solution. + For example, 1.0 liter of a 1.0M aqueous solution of NaCl has 1.0 mole of Na ions and 1.0 mole of Cl ions dissolved in it. As you may have noticed, water chemistry tends to use the units ppm or mg/L. You can convert between molar concentration units and parts per million using the following steps.

1.0 mol of Cl 1.0 M of Cl = 1.0 L of water 1.0 mol of Cl 35.45 g of Cl 1.0 L of water 1.0 mol of Cl

1000 mg 354500 mg 3.545 x 10 5 mg 5 = = 1.000 g 1.0 L of water 1.0 L of water = 3.5 x 10 ppm of Cl

Titrations & Total Water Hardness

Titration is a process that finds the concentration of a substance by reacting a solution containing it with a titrant, a solution of another substance of known concentration, until the precise point where all of the substance is gone. That point, referred to as the titration end point, is often represented visually by the addition of a reaction specific indicator, a substance that is added to a solution to follow the course of a titration, which is normally complete when the indicator changes color. In this activity the concentration of Mg and Ca ions was measured was measured through titration. 2+ 2+ The total water hardness simply reflects the total concentration of Mg and Ca ions. We normally, though, assume that CaCO3 is solely responsible for the water hardness. There is one mole of CaCO3 for 2+ 2+ each mole of Ca . The mass of CaCO3 is just the moles of Ca times the formula mass of one mole of CaCO3. Finally, the total water hardness is normally expressed in mg of CaCO3 per liter of water, so you must convert the molar concentration to ppm. The following sample problem represents the calculations you must perform in order to go from water sample and EDTA titrant to the total water hardness. A 0.020M solution of EDTA with EBT indicator was used to titrate 25.0mL of tap water. As the EDTA solution was added to the water, the indicator changed to a purple color. The EDTA was added until the entire solution turned to blue and the purple color was not visible in the solution. At the endpoint of this titration, it was found that 5.92mL of 0.020M EDTA had been added to the water. Calculate the mg/L of CaCO3 contained in the water, assuming that the water hardness was entirely due to this compound. It is given that 1 mol of EDTA titrates 1.0 mol of Ca , which is equivalent to 1.0 mol of CaCO3. Then
2+ 2+ 2+

1 mol CaCO 3 0.020 mol EDTA 3 4 2+ x 5.92 x 10 L solution x = 1.2x10 mol Ca 1 mol EDTA L so ln

The [CaCO3] in water =

1.2 x 10 4 mol CaCO3 2.5 x 10

2

= 4.8 x 10 M and in mg/L it would be:

4.8 x 10 3 mol CaCO3 100.1g CaCO 3 1000 mg x x = 480mg/L or 480ppm L g 1 mol CaCO 3
Subsequent activities will deal with ways in which the total water hardness can be reduced to prevent precipitation of soap scum. Water having a total hardness of less than 75 mg of CaCO3 per liter of water, is classified as soft, and water with a total hardness greater than 150 mg of CaCO3 per liter of water is classified as hard. Hard water is not a concern in some areas like the Northeast U.S. and the West Coast where rather insoluble granitic minerals are common. In the Midwest, though, sediments are mostly limestone, which is CaCO3. Needless to say, natural water supplies throughout the Midwestern U.S. are generally hard and basic. Bedrock, such as clay and some soils, also can produce water hardness associated with other anions, particularly sulfate and chloride.

Modern Methods of Analysis

Modern analytical methods generally utilize elaborate instruments for quantitative measurements, but the principles behind the operation of the instruments resemble those used in the simple comparisons carried out as part of this activity. You used an ion specific electrode to measure quantitatively the concentration of hydrogen ion, which must be monitored in a water treatment plants or any body of water that humans may swim, such as a pool, pond, or lake. Colorimetry also has a more high tech option. An optical instrument called a spectrophotometer can be used to measure amounts of substances based on the color of light that they absorb. Your activity uses 3+ 3+ the color of a complex formed when iron(III) (Fe ) binds to thiocyanate indicator ions to estimate the Fe concentration by comparing with standard solutions of known concentration. The spectrophotometer measures absorption of light of a specific wavelength by a sample, again in comparison with known standard solutions. The accuracy is much better but the same molecular property is the basis for both methods.

Total dissolved solids (TDS) used to be measured through a gravimetric method, based on weighing the solids after evaporation of all the water. Your teacher demonstrated a more convenient method for determining TDS by measuring the conductivity of the water, which is caused by dissolved ions. With 2+ 2+ + + some assumptions about which ions are responsible for most of the conductivity, i.e., Ca , Mg , Na , K , 2 HCO3 , SO4 , Cl and NO3 , the TDS can be calculated and used as a secondary standard to watch.

Questions: Quantifying Solutes

1. Return to the initial reading from your instructors total dissolved solids (TDS) demonstration in Preparing. Do you think any of the two or three solutes measured in class constitute a large percentage of the total dissolved solids for your specific water sample? If yes, which solute seemed to be the largest portion of the total dissolved solids? If no, what other ions do you predict are a large part of the TDS for your water sample? Explain your answer. 2. The maximum contaminant level (MCL) for nitrate ion in a water supply is 10.0 mg/L. a. Express this concentration in molar units (M). Show the work behind your calculations. b. If you measured nitrates, did your water sample meet this regulation? 3. The National Secondary Drinking Water Regulations (SDWR) from the U.S. Environmental 3+ Protections Agency recommend a level of Fe of 0.05 ppm. a. Express this concentration in molar units (M). Show the work behind your calculations. b. Did you water sample meet this regulation? 4. What chemical compounds are the sources of hardness in natural waters? 5. Water supplies having too much hardness can create soap scum and scale inside water heaters and water pipes. Offer reasons why dealing with these effects can be costly. 6. Total water hardness is calculated by making the assumption that most of the water hardness is due to calcium ions from calcium carbonate (CaCO3). For every one mole of calcium ion, there 4 would be one mole of calcium carbonate. Assume a 25.0mL water sample had 1.2x10 mol 2+ Ca . Calculate the total water hardness in ppm (mg/L) for this sample, assuming the water hardness is entirely due to CaCO3. Show your work completely.

7. Compare the total dissolved solids reading from What Do You Think? and the water hardness of your water sample. Which should be larger? Why? 8. The concentration of chloride ions (Cl ) in a water sample may be determined by titrating a water sample with a known concentration of silver nitrate (AgNO3) solution using sodium chromate (Na2CrO4) as an indicator. It is found that 7.0 mL of 0.010 M silver nitrate (AgNO3) is titrated into 10.0mL of a tap water sample to get the faint orange tint of silver chromate (Ag2CrO4) from the sodium chromate indicator. It is assumed that when this happens all of the chloride ion (Cl ) in + the tap water has now precipitated with the titrated silver ion (Ag ) as silver chloride (AgCl).

a. What is the equation for precipitating the chloride ion with the silver ion? b. How many moles of silver ion were titrated into the sample of tap water? Show your work. c. How many moles of chloride ions were present in this tap water solution? d. What is the molar concentration (M) of the chloride ions in the tap sample? e. How many ppm (mg/L) of chloride ions are in the tap water sample? 9. Is the pH of your sample of tap water within the Secondary Drinking Water Standard pH range of 6.5-8.5? What are the molarities for hydrogen ion associated with a pH of 6.5 and a pH of 8.5? 10. If a solution has a hydrogen ion concentration of 1.0 x 10 M what is the pH? 11. If a solution has a hydrogen ion concentration of 1.5 x 10 M a. What is the pH? b. Does it have more or less hydrogen ions than a neutral solution?
-4 -7

c.

Is it an acid or a base?

CT

C R I T I C A L L Y

T H I N K I N G

MEAN? KNOW? BELIEVE? CARE?

What does the activity mean?

Chemistry explains the macroscopic phenomenon (what you observe) with and explanation of what happens at the nanoscopic level (atoms and molecules) using symbolic structures as a way to communicate. Explain the meaning of this activity by completing the MNS table. M ACRO Explain how colorimetry works to determine an unknown concentration of an ion. N ANO Describe (with a nanoscale picture) a titration. SYMBOLIC What is the dilution equation? In words, describe how to use it to make a dilution.

How do I know?
Making specific reference to your data, observations, and the terms from this activity, how explain how an indicator helped you know the concentration of various solutes in each procedure.

Why do I believe?
Continuing to review, name two concepts from a previous unit that you needed to know in order to solve How Much. How specifically does each concept inform (or help you solve for) How Much?

Why do I care?
We are going to start to look at solubility changing. Two things that can change the amount of solute able to dissolve in solution are pH and temperature. On the Internet, look up solubility curves (do a Google image search for solubility curve temperature and solubility curve pH). Save a few to your computer and note the following for this question: a. Define solubility. b. In general, as temperature increases, what happens to the solubility of ionic compounds? What is an exception? c. As temperature increases, what happens to the solubility of gasses? d. What is the solubility of ammonium chloride at 50C? e. What is the solubility of ammonia at 50C? f. When are heavy metal ions of concern (copper, nickel, cadmium, lead) more soluble, in acidic or basic environments (pH of 4 or pH of 10)?

g. In terms of your challenge, to assess and purify the water of a developing nation, why does this matter?