Name: ___Hayden Robbins______________ 9-19-2017

Experiment 3
Hardness Lab

OBJECTIVES
1) To analyze hardness in water samples
2) To remove hardness using ion exchange resins.

INTRODUCTION

Hardness
Water hardness is defined as the sum of normalities of all multivalent cations (i.e., charge of +2 or
greater). Hardness is a concern in municipal water supplies. Water that is too hard has a tendency to
form solid precipitates known as scale that deposit on the inner surface of pipes and fittings. Excessive
scale can seriously impede water flow through a distribution system. On the other hand, the deposition of
some scale in pipes is desirable as a preventive measure against corrosion (Hardness of municipal water
supplies is also an aesthetic concern: Solid precipitates from hard water can accumulate on bathroom
surfaces and cookware. Soap does not form a good lather in hard water.
Usually, the main cations that contribute to drinking water hardness are Ca 2+ and Mg2+, but in some
circumstances Fe3+ and Al3+ can also important.
The primary measurement unit for expression hardness is normality (or ionic charge per volume), that
is, equivalents per liter. In engineering practice, hardness is often expressed in terms of the equivalent
mass concentration of calcium carbonate (CaCO3) that, dissolved in pure water, would produce the same
hardness as found in the sample of interest. Given that CaCO3 has a molecular weight of 100 g/mol and
that each mole of CaCO3 liberates two moles of cationic charge, the unit conversion is easy: A hardness
of 1 meg/L is the same as a hardness of 50 mg/L as CaCO3 as shown in Table 1.

Table 1 Hardness Classification of Water

Classification Hardness (meq/L) Hardness (mg/L as CaCO3)

Soft < 1.5 < 75
Moderately hard 1.5-3 75-150
Hard 3-6 150-300
Very hard >6 >300

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 The hardness of water depends on contact with dissolvable minerals, among other factors. For
example, water from freshly melted snow tends to be soft whereas groundwater tends to be hard or very
hard.
The hardness of water is sometimes subdivided into carbonate and noncarbonate hardness. This
division can be confusing because it does not depend on the hardness ions themselves, but rather on the
anions present in solution. Conceptually, the difference between carbonate and noncarbonated hardness
lies in the form of the solids that dissolved to generate the hardness. For example, carbonate hardness
can be generated by the dissolution of calcium carbonate or magnesium carbonate, whereas
noncarbonate hardness can be generated by the dissolution of calcium sulfate, calcium hydroxide, or
calcium chloride. The distinction is important when chemical precipitation is used to remove hardness.

Ion Exchange
As the name suggests, ion exchange functions by removing some ions from water in exchange for
others. A net benefit can be realized if the removed ions are more harmful, more hazardous, or less
desirable than the replacements.
Ion exchange occurs on the surface of certain solids. Zeolites, natural clay minerals, were the first
materials used for ion exchange in water treatment. Most applications now use synthetic materials such
as resin beads. The ion exchange properties of these resins are a result of surface molecules added
during manufacture.
Water softening is an important technological application of ion exchange. However, ion exchange is
not typically used for softening in large water treatment plant because it is more expensive than the lime
soda process.
Consider the case of calcium removal using a strong-acid cation exchanger. If the active ion
exchange sites are sulfonates initially charged with sodium, the exchange reaction may be written in this
form:
2≡SO3Na + Ca2+  (≡SO3)2Ca + 2 Na+

Where ≡SO3 represents a sulfonate group attached to the resin surface. In the forward direction, two
surface groups release their attached sodium ions into solution in favor of binding one calcium ion.
When unspent resin is exposed to ordinary water, the forward direction of the reaction is strongly
favored. Many other cations will also be preferentially bound on the surface in exchange for sodium.

APPARATUS
1. Magnetic stirrer and magnet bar
2. Glassware

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 REAGENT

Hardness Experiment
1. water samples
2. Buffer solution obtained from HACH hardness analysis kit. The buffer solution is also prepared by
dissolving 16.9 grams of NH4Cl in 143 mL of NH4OH (concentrate) solution with additional of 1.25
grams Mg-EDTA and brought to the final volume of 250 mL using DI water. On the other hand,
the buffer solution can be prepared using 1.179 gram of Disodium EDTA Dihydrate and 780 mg
of MgSO4 7H2O in 50 mL DI water. Then, transfer the solution into 16.9 gram of NH4Cl in 143 mL
of NH4OH (concentrate) and brought to the final volume of 250 mL using DI water.
3. Eriochrome Black T indicator: mix 0.5 gram of Eriochrome Black T and 4.5 of Hydroxylamine
Hydrochloride with additional of 100 mL of 95% ethanol.
4. Titrant: 0.01 EDTA solution. Add 3.723 grams of EDTA in 1000 mL of DI water.

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PROCEDURE

Task 1 Determine hardness in each water samples

Determine hardness of three unidentified water samples

1. Pipette 5.00 mL of each water sample in a flask

2. Add 3 drops of buffer solutions and 1-2 drops of Eriochrome Black T (indicator)
3. Titrate the water sample with 0.005 M EDTA solutions until the color change from purple red to blue.
4. Record volume of EDTA used for titration
5. Total hardness (mg/L of CaCO3) = [A × M × 100 × 1000 ] / B
When A = Volume of EDTA used in titration (mL)
B = Volume of water sample
C = EDTA concentration in molar
Volume of water use _____5____ mL
Concentration of EDTA ___0.005____ M

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Table 2 Total Hardness Concentration in Each Sample
Volume of Water Used 5.000 ml
Concentration of EDTA 0.005 N

Sample Name EDTA Read EDTA Read after EDTA Volume Total
before Titration used for Hardness
Titration Titration (mg/L of
CaCO3)
Deionized Water 40.09 40.19 0.10 10.00
Crystal Geyser 40.19 41.01 0.82 82.00
Evian 41.01 43.20 2.19 219.00
Arrowhead 43.02 45.30 2.28 228.00
Tap Water 45.30 46.80 1.50 150.00

Table 3 Total Hardness Concentration after Ion Exchange - PFR

Volume of Water Used 20.00 ml
Concentration of EDTA 0.005 N

Resins (grams) EDTA Read EDTA read after EDTA volume Total Hardness
before Titration (purple red to used for hardness Removal
Titration (mL) blue) (mL) Titration (mL) (mg/L of (%)
CaCO3)
0.00 38.20 38.20 0.00 0.00 100.00
0.50 38.20 40.93 2.73 68.25 16.77
2.00 25.60 27.95 2.35 58.75 28.35
5.00 27.95 28.95 1.00 25.00 69.51
10.00 40.93 41.21 0.28 7.00 91.46

Table 4 Total Hardness Concentration after Ion Exchange - CSTR

Volume of Water Used 20.00 ml
Concentration of EDTA 0.005 N

Resins (grams) EDTA Read EDTA read after Titration EDTA volume Total Hardness
before (purple red to blue) (mL) used for hardness Removal
Titration Titration (mL) (mg/L of (%)
(mL) CaCO3)
0.00 10.40 14.10 3.70 92.50 -12.80
0.50 41.21 43.72 2.51 62.75 23.48
2.00 28.95 31.40 2.35 58.75 28.35
5.00 11.10 13.45 2.35 58.75 28.35
10.00 13.45 16.15 2.70 67.50 17.68

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Discussion:
1. Report hardness concentrations from Table 2 (write it out). Do you think your results are
reasonable? Why?
Table 2 shows that the hardness concentration of the Deionized Water was 10.00 mg/L, Crystal
Geyser was 82.00 mg/L, Evian was 219.00 mg/L, Arrowhead was 228.00 mg/L and the Tap
Water was 150.00 mg/L. These results are deemed reasonable based on the knowledge that
Crystal Geyser, Evian, and Arrowhead are all spring water samples. Spring water samples are
naturally hard, respectively. Based on the data obtained, it can be noted that Arrowhead water is
the hardest, Evian water is moderately hard, and Crystal Geyser is the least hard out of the three.
Deionized water is soft and tap water is moderately hard. These values reflect the respective
range of hardness concentrations for these samples.
2. Discuss the relationship between alkalinity and hardness in each sample (you need data
from alkalinity lab).
Due to the lack of alkalinity values within the water samples tested in Lab 2, it is difficult to
determine how alkalinity and hardness are related based on the data collected. One thing that
can be noted is the only samples that displayed any alkalinity, Tap and Arrowhead, had relatively
high hardness concentrations, Arrowhead being the highest out of all the samples.
3. Plot 2 graphs (chart title, axis titles, units, legends must be displayed).
a. Results from Table 2 using bar graphs.

TOTAL HARDNESS
CONCENTRATION FOR EACH
250.00
Conentration (mL)

200.00
150.00
100.00
50.00
0.00
Deionized Crystal Evian Arrowhead Tap Water
Water Geyser
Sample Name

EDTA Read before Titration EDTA Read after Titration

EDTA Volume used for Titration Total Hardness (mg/L of CaCO3)

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 b. Results from Table 3 and 4 in one graph using scattering with manual trend lines
when x-axis is mass of resins and y-axis is the % hardness removal.

MASS OF RESINS VS. HARDNESS

REMOVAL
120.00
HARDNESS REMOVAL (%)

100.00

80.00
PFT
60.00
CSTR
40.00
Expon. (PFT)
20.00 Expon. (CSTR)
0.00
0.00 2.00 4.00 6.00 8.00 10.00 12.00
MASS OF RESINS (GRAMS)

4. Compare the hardness removal (%) from Part 2 (PFR) and Part 3 (CSTR)
a. Both have the similar removal efficiency? How do you justify?
Based on the data, the removal efficiencies of 0.5 grams – 2.00 grams of resin is
relatively similar between both of processes. Once the value of resin increases above
2.00 grams, the PFR process provides a more efficient way of removal, with the highest
percent of removal at 91.46%
b. If not, which process is better?
By comparing Tables 3 and 4, it can be proven that at higher resin amounts (< 2.00
grams), the PFR process is more effective at removing hardness than the CSTR process.
c. What factor contributes to the better hardness removal performance?
Better hardness removal performance can be contributed to short circuit and contact
time.
d. What is the typical hardness concentration in the tap water in our area (provide
reference)?
For Long Beach, the typical hardness concentration in tap water is 18 grains per gallon,

Reference: http://www.lbwater.org/sites/default/files/documents/2016_WQ_Report.pdf
e. What is the suggested hardness concentration in drinking water (provide
reference)?
In the most recent Water Report for the city of Long Beach, the suggested hardness
concentration in drinking water should range from 17-19 grains per gallon.

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 Reference: http://www.lbwater.org/sites/default/files/documents/2016_WQ_Report.pdf
f. What are the health effects of drinking water with high hardness concentration for
a long time (provide reference)?
Most studies show that there are no negative health effects of drinking water with high
hardness concentration, instead, hardness in water can be beneficial to dietary intake.
Counters to this opinion claim that high hardness contributes cardiovascular mortality, but
there is not enough sufficient data to back it up.s
Reference: http://www.who.int/water_sanitation_health/dwq/chemicals/hardness.pdf
g. Can we drink tap water regularly? Do we need to remove hardness in tap water
before drinking?
h. If you need a design a water softening system for 200ml, can your results provide
the optimal amount of resins required? What is that amount?

5. Provide calculation samples (2; one for hardness and one for removal)

Pick only Task 2 or 3.

Task 2 Remove hardness using ion exchange resins-PFR

1. Take 4 cylinder tubes. Put 3 filters at the end with cushion.

2. Add 0.5000, 1.0000, 2.0000, 5.0000 and 10.000 grams of cation exchange resins into each tube.
3. Add cushion on the top of the resins.
4. Pour 200.00 ml of Crytal Geyser water into each tube with resins.

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5. Collect 20.00 ml of the effluent and analyze hardness.

Table 3 Total hardness concentration after ion exchange-PFR

Volume of water use __________________ mL
Concentration of EDTA _______________ M

Resins EDTA Read before EDTA read after ETDA volume used Total Hardness
(grams) Titration Titration for titration hardness removal (%)
(ml) (purple red to blue) (mL) (mg/L of CaCO3)
(ml)

Hardness for each water sample.

Graph here

Figure 1 Hardness concentration in each water sample

Task 3 Remove hardness using ion exchange resins-CSTR

1. Take 5 flasks.
2. Add 0.5000, 1.0000, 2.0000, 5.0000 and 10.000 grams of cation exchange resins into each flask.
3. Add cushion on the top of the resins.
4. Pour 200.00 ml of Crytal Geyser water into each tube with resins.
5. After 10 mins. collect 20.00 ml of the effluent and analyze hardness.

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Table 4 Total hardness concentration after ion exchange-CSTR
Volume of water use __________________ mL
Concentration of EDTA _______________ M

Resins EDTA Read before EDTA read after ETDA volume used Total Hardness
(grams) Titration Titration for titration hardness removal (%)
(ml) (purple red to blue) (mL) (mg/L of CaCO3)
(ml)

Percent removal of PFR VS CSTR (graph- 2 lines)

Graph here

Figure 2 Percent hardness removal for plug-flow reactor (PFR) and continuous stirred tank reactor
(CSTR)

After experiment (Discussion)

1. Report hardness concentrations from table 2 (write it out). Do you think your results are
reasonable? Why?

2. Discuss the relationship between alkalinity and hardness in each sample (you need data from
alkalinity lab).

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3. Plot 2 graphs (chart title, axis titles, units, legends must be displayed)
a. Results from table 2 using bar graphs.
b. Results from table 3 and 4 in one graph using scattering with manual trend lines when x-
axis is mass of resins and y-axis is the % hardness removal.

4. Compare the hardness removal (%) from Part 2 (PFR) and Part 3 (CSTR)
a. Both have the similar removal efficiency? How do you justify?
b. If not, which process is better?
c. What factor contributes to the better hardness removal performance?
d. What is the typical hardness concentration in the tap water in our area (provide
reference)?
e. What is the suggested hardness concentration in drinking water (provide reference)?
f. What are the health effects of drinking water with high hardness concentration for a long
time (provide reference)?
g. Can we drink tap water regularly? Do we need to remove hardness in tap water before
drinking?
h. If you need to design a water softening system for 200 ml, Can your result provide the
optimal amount of resins required? What is that amount?

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