Name: Chryzl D.

Suobiron 2013 Course/yr: BS ChE - IV 2013

Date Date

performed:Jan. submitted:Jan.

12, 21,

Experiment #1 Water Hardness and Conditioning I. Introduction: Water may look pure and refreshing, but the truth is that water contains many chemicals and impurities. When water evaporates from the earth, it rises into the atmosphere and forms into cloud formations. Under certain conditions, it then returns to earth in the form of rain, snow, sleet or hail and may also appear as dew or fog. As moisture falls from the sky, it can pick up minerals, gasses, solids and chemicals, and bacteria. As it runs over the ground, it picks up additional organic contaminates from the earth's surface. As the water seeps into the ground, it then picks up other contaminates, such as calcium, iron, magnesium and hydrogen sulfide. As the water dissolves mineral deposits in the stratus of the earth leaving excessive levels of calcium and magnesium the water becomes hard chemically. Hard water can produce a rocklike scale that builds up in pipes, mixers, heaters, machines and other equipment especially in chemical processing industries. This scale can also reduce water flow and clog valves and pipes to create maintenance problems and reduce the life of equipment. Hard water reduces the ability of soap to clean and produce suds, leaving a residue or precipitates. It does not only attack industries but even homes. Hard water is more abrasive than soft water. The mineral particles combine with soap used at home to become little pieces of rock pounding away at clothing fibers and fragile glassware. Glasses become etched and the life of clothing is reduced. Skin and hair are affected by hard water as well. A greater amount of shampoo and soap is needed to clean, and hard water doesn't rinse off as well as soft water. That means soap residues remain,

leaving skin susceptible to blemishes and hair less shiny. Water hardness is the most common of all water problems. The presence of calcium and magnesium salts cause water to be hard proportional to the quantity of the heavy metals that are present. The most common method of designating the degree of hardness of a given
GRAINS PER GALLON Less than 1.0 1.0 to 3.5 3.5 to 7.0 7.0 to 10.5 10.5 and Higher DEGREE OF HARDNESS Soft Slightly Hard Moderately Hard Hard Very Hard

water supply is in grains per gallon (GPG). Here is what an analysis in grains per gallon means to you, according to the U.S. Department of the Interior and Water Quality Association Standards:

Water softening or conditioning, on the other hand, will solve your hard water problem. Water is softened or conditioned by replacing hardness ions such as calcium and magnesium with softer sodium or potassium ions as the most effective and common conditioning. Water softeners must be regenerated regularly with a brine solution, renewing their ability to remove hardness from water. The hard water is passed through a tank containing resin beads coated with sodium ions or potassium ions. The calcium and magnesium ions are exchanged for the sodium ions, thus conditioning the water. When the beads have trapped all the hardness they can hold, the unit is regenerated with salt brine to replace the hardness ions with sodium ions. The unit is then ready to condition water again. Two Types of Water Hardness 1. Temporary hardness -Also known as carbonate, this type of hardness is caused by bicarbonates of calcium and magnesium. 2. Permanent Hardness

-Known as noncarbonate, this type of hardness is due to the sulfates and chlorides of calcium and magnesium. Water Conductivity Conductivity is a measure of the ability of water to pass an electrical current. Conductivity in water is affected by the presence of inorganic dissolved solids such as chloride, nitrate, sulfate, and phosphate anions (ions that carry a negative charge) or sodium, magnesium, calcium, iron, and aluminum cations (ions that carry a positive charge). Since the presence of salts such as calcium and magnesium triggers the electrical current to pass, it follows that the harder the water it is more conductive. Conductivity is also affected by temperature: the warmer the water, the higher the conductivity. For this reason, conductivity is reported as conductivity at 25 degrees Celsius (25 C). Conductivity in streams and rivers is affected primarily by the geology of the area through which the water flows. Streams that run through areas with granite bedrock tend to have lower conductivity because granite is composed of more inert materials that do not ionize (dissolve into ionic components) when washed into the water. On the other hand, streams that run through areas with clay soils tend to have higher conductivity because of the presence of materials that ionize when washed into the water. Ground water inflows can have the same effects depending on the bedrock they flow through. The basic unit of measurement of conductivity is the mho or siemens. Conductivity is measured in micromhos per centimeter (mhos/cm) or microsiemens per centimeter (s/cm). According to Environmental Protection Agency (EPA), Pure or purified water is not a good conductor of electricity so its conductivity is expected to be the least among others. Distilled water has conductivity in the range of 0.5 to 3 mhos/cm. The conductivity of rivers in the generally ranges from 50 to 1500 mhos/cm. Studies of inland fresh waters indicate that streams supporting good mixed fisheries have a range between 150 and 500 hos/cm. Conductivity outside this range could indicate that the water is not suitable for certain species of fish or macroinvertebrates. Industrial waters can range as high as 10,000 mhos/cm. Sea water can have 50000 mhos/cm

Soap Test The volumes of soap solution needed give a measure of the relative hardness of the water. With more able groups, it might be worth considering that pure water is completely soft, so that the volume of soap required here is just the amount required to get a lather, not to overcome hardness. The volume obtained should be subtracted from the other volumes before the relative hardnesses are compared. Hard water contains dissolved calcium (or magnesium) salts that react with soap solution to form an insoluble scum that should be seen as a white cloudiness in the tubes: calcium salt(aq) + sodium stearate (soap)(aq) calcium stearate(scum)(s) + sodium salt(aq) Only when all the calcium ions have been precipitated out as scum will the water lather. Thus the volume of soap solution measures the amount of hardness and it implies that the harder the water the more precipitated calcium ions will form. In hard water, soaps exchange their cations for the hard water cations, and the resulting complex is insoluble, precipitating from the water. That means that it will not work to lower the water's surface tension because the soap no longer has a hydrophilic head. Detergent Test Detergent has a special substance in it called sodium zeolite A which takes the calcium and magnesium ions out of hard water. These ions prevent the soap in the water from bubbling. In the hard water, the detergent should bubble better than the soap. One can determine if a tap water is hard or not by seeing how well soap bubbles in it. Heating Method Heating can be done only in water with temporary hardness and not for those permanent ones. Temporarily hard water is defined as that which can be softened by boiling. On boiling, the reaction in softening the water: Ca(HCO3)2(aq) CaCO3(s) + CO2(g) + H2O(l)

Permanently hard water contains calcium or magnesium salts other than the hydrogen carbonates. These are unaffected by boiling. As shown in the reaction of hydrogen carbonates it is just but the reverse of boiling. CaCO3(s) + CO2(g) + H2O(l) Ca(HCO3)2(aq) (Calcium hydrogen carbonate) Cold-lime Method Precipitation softening accomplished at ambient temperatures is referred to as cold lime softening. When hydrated lime, Ca(OH)2, is added to the water being treated, the following reactions occur: CO2 +Ca(OH)2 =CaCO3 +H2O Ca(HCO3)2+Ca(OH)2 =2CaCO3 +2H2O

Mg(HCO3)2+2Ca(OH)= Mg(OH)2 +2CaCO3 +2H2O If the proper chemical control is maintained on lime feed, the calcium hardness may be reduced to 35-50 ppm. Magnesium reduction is a function of the amount of hydroxyl (OH-) alkalinity excess maintained. Noncarbonate or permanent calcium hardness, if present, is not affected by treatment with lime alone. If noncarbonate magnesium hardness is present in an amount greater than 70 ppm and an excess hydroxyl alkalinity of about 5 ppm is maintained, the magnesium will be reduced to about 70 ppm, but the calcium will increase in proportion to the magnesium reduction. Ion Exchange Method All water softeners use the same operating principle, trading minerals in a process called ion exchange. The zeolite/resin carries a negative charge and the offending minerals carry a positive charge. The positive charged mineral ions exchange places with the weaker positively charged sodium ions and are held fast in the zeolite until they themselves

are knocked off during the recharge cycle. After recharging, the zeolite is cleaned of the bad minerals and reunited with its slightly positive friend the sodium ion and ready to attract more minerals in the water stream. The essential part of a water softener is the mineral tank that holds the negatively charged resin/zeolite beads. Calcium, magnesium and sodium (the minerals that make your water hard) carry positive charges with sodium holding the weaker charge of the three. As the water moves through the tank, the minerals will displace the weaker charged sodium ions and become entrapped in the zeolite. If all is working correctly, after the zeolite bed is completely saturated, the unit will recharge itself with a strong brine (salt) solution. The force and strength of the solution knocks the minerals off the beads and reseats the sodium ions back into the zeolite beads. Other Softening Processes Other processes can be used to soften water, but they are generally expensive and only used in rare circumstances. These alternative processes are listed below. Reverse-osmosis softening involves water being forced through a semi-permeable membrane. Calcium, magnesium, and dissolved solids are captured while the softened water is passed through the membrane.

Electrodialysis involves passing water between two plates with opposite electrical charges. The metals in the water are attracted to the plate with the negative charge while the non-metals are attracted to the plate with the positive charge. Both types of ions can be removed from the plates and discarded. Electrodialysis is used on very hard water, with a hardness of more than 500 mg/L as calcium carbonate.

Distillation involves the evaporation of water. The evaporated water leaves behind all hardness compounds, softening the water.

II.

Objectives: 1. To measure and compare qualitatively and quantitatively the hardness of different water sources. a) Conductivity Test b) Soap and Detergent Test 2. To perform and evaluate the different water softening methods. a) Heating b) Lime Process c) Ion Exchange

III. Materials and Apparatus: Materials: detergent powder, soap, lime powder, water (from different sources) No. 1 2 3 4 List Amount (li) 1.5 1.5 1.5 1.5 of Water Samples Used Water Sources Distilled Water Deep Well River Canal Origin

CPU Jaro Jalaur River CPU-Uy

5 1.5 Deep Well Sta. Barbara 6 1.5 Creek Lambunao 7 6 Seawater Guimaras Strait 8 1.5 Brackish Dumangas 9 1.5 Purified Water Rain Dew 10 1.5 Rainwater Jaro 11 1.5 Tap Water CPU-Engineering Table 1 List of water sources and their origin, including the amount (li) used in the experiment. Apparatus: beakers (8), glass stirring rod, graduated cylinder, conductivity meter, hot plate, Erlenmeyer flask, mortar and pestle, stop watch, spatula IV. Procedure: Each student was tasked to bring water samples from different water sources as shown in Table 1. A 200ml water sample was put into a container (preferably a beaker or an Erlenmeyer flask) that was taken from the prepared 1.5li of different water sources. After all materials were ready for the said experiment, the students started the different tests which included: the measure of hardness (quantitative and qualitative) conductivity test, soap test and detergent test, the softening methods heating, cold-lime process and ion exchange. For quantitative test, the conductivity of each water sample from different water sources was recorded using a conductivity meter for future comparisons and as well as a basis of the hardness of the different samples in the different following tests. For soap test, a 200ml of water from different water sources was placed in their respective beakers/Erlenmeyer flasks. An equal amount of soap using a spatula was placed in each beaker and was stirred for 2 minutes at the same time. After stirring the mixture was left to settle any precipitates formed. After a while the students were then asked to observe the mixtures according to its appearance and texture that would indicate their individual hardness compared to others. In a different beaker, another 250ml of different water sources was prepared for the detergent test. Equal amount of detergent powder using a spatula was placed in each beaker. Using the stirring rod, the mixture was stirred for two minutes and was observed. The intensity

of stirring as much as possible should be the same. Since there were only small significant differences found in each mixture, another spatula of detergent powder was placed for visible results. It was again stirred for two minutes and let the precipitates settle. All observations in the appearance and texture were carefully recorded. After measuring the hardness of water quantitatively and qualitatively, the test for softening the water followed. The first test was heating the water sample. 500ml from each water sample was placed into a beaker/Erlenmeyer flask and was heated in a hot plate until precipitates was formed. This method was done before any other tests since it required enough time to boil and form the precipitates that would indicate the minerals present in the sample contributing to water hardness. The next test was the cold-lime softening which requires the addition of lime powder in the water. Only three water sources were picked to undergo this test. In three different beakers an amount 420ml of deep well water (Jaro), 450ml of brackish water (Dumangas) and 450 ml of seawater (Guimaras Straight) was poured. One spatula of lime powder was poured into each beaker. Using a stirring rod, the mixture was stirred at the same time with the same intensity until the lime dissolved in the water. Observations were then recorded after the test. The last test performed was the ion-exchange softening which was done only for the water sample coming from the deep well (Sta. Barbara) since the color of the water was yellowish brown. 400ml of the said water sample was prepared for the test. Before the test, the ion-exchange apparatus was cleaned by pouring the remaining seawater or the brine solution available from the top of the apparatus until the cation resin was colored light brown. After that the water sample to be used was poured the same manner as the brine. The effluent of the ion exchange apparatus was then observed and tested further. After performing the tests, all materials and apparatus used was carefully cleaned and stored. All water samples were disposed properly. V. Observations, Result and Analysis:
Water Conductivity

Water Sources Rainwater Purified Water Distilled water River Deep well Creek Canal Tap Water Deep well Brackish water Seawater

Origin Jaro Raindew CPU Jala-ur River Jaro Lambunao CPU-Uy CPU-Engineering Sta. Barbara Dumangas Guimaras Strait

Conductivity ( ) 44.1 85.6 87 610 1043 1055 1105 1247 1769 47,700 49,600

Temperature (C) 26.5 27.3 26.7 26.8 27 27 27.5 27.4 27.1 27.1 26.9

Table 2 Water conductivity of the water samples from different water sources at 26-28C arranged from least to most conductive. The table above shows the conductivity of different water sources arranged from the least to the most conductive at certain temperatures. It can be observe that the rainwater is the least conductive having a conductivity of 44.1 compared to the seawater as the most conductive with 49,600 . As stated in the theoretical framework, according to EPA purified water should be the least conductive however for sea water it is true that it should have the highest conductivity. It can also be observed that brackish water conductivity is near to seawater since according to their strategic locations brackish water was just an extension of the sea. Pure and distilled water also have almost the same conductivity since one way of purifying water is through distillation also.
Soap Test Water Sources Rainwater Purified Water Distilled water River Deep well Creek Origin Jaro Raindew CPU Jala-ur River Jaro Lambunao Appearance
Very cloudy, w/ large amount of bubble formation Cloudy,w/ small amount of bubble formation Cloudy, no bubble formations Cloudy, no bubble formations cloudy no bubble formations Less cloudy, w/ undissolved

Texture Smooth Smooth Smooth Smooth Smooth Smooth

soaps but no bubble formations Less Cloudy, w/ undissolved soaps but no bubble formations Less Cloudy, w/ undissolved soaps but no bubble formations No visible effects, undissolved soap No visible effects, undissolved soap No visible effects, undissolved soap

Canal

CPU-Uy

Smooth

Tap Water Deep well Brackish water Seawater

CPUEngineering Sta. Barbara Dumangas Guimaras Strait

Smooth Not so smooth Not so smooth Not so smooth

Table 3 Soap test observations The table above shows the observations according to appearance and texture of the mixture. From the recorded data, rainwater dissolved the soap forming a cloudy mixture that when settled will turned out to be a precipitate. Rainwater also obtained the highest formation of bubbles compared to other mixtures and provided a smooth texture as what others also have. On the other hand the last three sources in the table do not give any change in appearance and undissolved soap was found at the bottom of the mixtures. The last three sources do not also exhibit any significant changes in texture as what the others provided. The provided results coincide with the theory stated above wherein soft water will most likely to precipitate compared to hard water using a soap.
Detergent Test Water Sources Rainwater Purified Water Distilled water River Deep well Creek Canal Jaro Raindew CPU Jala-ur River Jaro Lambunao CPU-Uy Origin Appearance
Many bubbles formed No bubbles formed Many bubbles Many bubbles Small amount of bubbles Small amount of bubbles Small amount of

Texture Mild Slippery Slippery Mild Slippery Mild Slippery Slippery Slippery Slippery

bubbles

Tap Water Deep well Brackish water Seawater

CPU-Engineering Sta. Barbara Dumangas Guimaras Strait

Small amount of bubbles No bubbles Many bubbles Many bubbles

Slippery Slippery Very Slippery Very Slippery

Table 4 Detergent test observations As shown in the table above, it can be observed that there are some inconsistencies found in the results. It was stated in the procedure that the stirring should be of equal intensity and the soap should be of equal amounts. However, different individual stir the mixture and no fix amount in grams of the detergent added was measured thus contributing to an inaccurate result. Discrepancies in the bubble formation in different water samples can also be observed since aside from beakers, Erlenmeyer flask were used so not enough air was supplied for the formation of the bubbles. According to the observations given, detergent dissolved readily in both brackish water and seawater giving a very slippery texture. It shows that no bubbles formed in water sources coming from deep well (Jaro) and purified water which in fact their hardness according to conductivity is far from each other. According to the theoretical framework provided above, a detergent should be dissolved readily in hard water compared to soft water.
Water Sources River Deep well Creek Brackish water Seawater Heating Softening Method Origin Appearance Jala-ur River Jaro Lambunao Dumangas Guimaras Strait
Less precipitate formed Precipitate formed Precipitate formed More precipitate formed More precipitate formed

Table 5 Heating softening method observations According to the table above seawater and brackish water formed precipitates the most compared to others. Theoretically, hard water contains large amounts of

salts that when heated forms precipitate at the bottom of the container. These precipitates were the salts contained in a hard water, thus once it is removed the said water will most likely become soft. The observations above followed the said principle on heating hard water.
Water Sources Deep well Brackish water Seawater Cold-lime Softening Method Origin Appearance Jaro Less clear with undissolved solids Dumangas Clear with undissolved solids Guimaras Strait Clear with undissolved solids

Table 6 Cold-lime softening method observations According to the table above, all water samples becomes clearer compared to the original samples however there were still some solid particles found at the bottom of the container since there were no fix amount in grams of lime added in each container. The removal of turbidity in water samples implies softer water since the salts are captures in limewater upon the addition of lime in the water.
Water Sources Deep well Ion-Exchange Softening Method Origin Appearance Conductivity( Sta. Barbara Before: yellowish brown After: Colorless Before: 1760 (at 27.4 C) After: 2220 (at 27.8 C)

Table 7 Ion-exchange softening method observations As shown in the table about ion-exchange method results shows that the appearance and conductivity, before and after the softening process produced a significant difference. The yellowish-brown appearance of the water before was turned into colorless which implies the removal of metals that contribute to the color of the water. There was also a significant difference in conductivities since it becomes higher after the softening method. The according to the theories provided above, the conductivity should be lower than the original. Discrepancy in conductivity was actually due to the brine solution that was used to

clean the ion-exchange apparatus. There were probably remaining salts in the apparatus that was carried away by the sample water during the test resulting to a higher conductivity. VI. Conclusions and Recommendations: The hardness of water from different water sources can be measure and compare qualitatively and quantitatively was using conductivity test, and soap and detergent test. Using the conductivity test, it shows that the higher the conductivity, the harder will be the water. On the other hand using the soap test, it implies that the softer the water the more it readily reacts with the soap forming precipitates. However, using the detergent test, hard water performs best. Different softening methods such as heating, lime process and ion-exchange method can be applied for hardness removal. Heating method which works best for water with temporary hardness is a convenient way of softening hard water by precipitating out salts through boiling. Lime process works best by dissolving out salts using lime in a homogeneous solution. The ion-exchange method would be a good softening method especially in decolorization of water. The use of other softening methods available such as reverse osmosis, electrosialysis, and distillation would be highly recommended in future experiments regarding hard water for comparison. It would also be best if other methods in determining water hardness such as EDTA or Ethylenediaminetetraacetic acid to form CaEDTA or MgEDTA. The end point of EDTA titration shall determine how much of the Ca and Mg ions are being reacted thus the amount of hardness can be calculated. Materials used should also be of fix amount especially in addition of lime, soap and detergent.

VII.

References:

Online:(Retrieved: Jan. 20, 13)

1. 2. 3. 4. 5. 6. 7. 8.

http://www.ecowaterusa.com/faqs.php http://www.stevenswater.com/water_qualit y_sensors/conductivity_info.html http://www.lenntech.com/applications/ult rapure/conductivity/water-conductivity.htm http://water.epa.gov/type/rsl/monitoring /vms59.cfm http://www.nuffieldfoundation.org/practi cal-chemistry/testing-hardness-water www.mrsec.psu.edu people.cedarville.edu http://www.gewater.com/handbook/ext_trea tment/ch_7_precipitation.jsp#Cold lime softening

Book: (Retrieved: Jan 19,13) 1. Austin, G. T. (1984). Shreves Chemical Process Industries, 5th ed. McGraw-Hill Company. Singapore.