INORGANIC CONSTITUENTS OF WATER

BONDING REVIEW Valence electrons the electrons in the outer shell orbital of elements Inert atoms - full outer orbitals (far right column in periodic table) All other atoms - not completely happy, must bond with other atoms to be stable e.g. H

1 free outer shell electron

Cl

7 outer shell electrons, 1 free (not paired) electron

C 4 outer electrons, all not paired, thus free to bond every carbon atom must

bond to four other atoms to be stable

O or O

6 outer shell electrons 2 free to bond

5 outer shell electrons, 3 free to bond

5 outer shell electrons, 3 free to bond

Ionic bond - transfer of electron from one atom to another atom e.g. NaCl

Na + Cl

Na+ +

: Cl :

Na has 1 less e- therefore a + charge Cl has 1 extra e- therefore a - charge

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Covalent bond - pair of electron with opposite spins that is shared by two atoms e.g. H2 H + H H:H (H-H) e.g. CH4 H C + 4 H H C H H

H C H

special cases e.g. Nitrogen H H: N :H

Ammonia

NH3 not charged

Ammonium

H H: N :H H+

NH4+ has a plus one charge

This is just a short review, read your Chemistry notes if you need more

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INORGANIC WATER QUALITY

Major ionic species in water Cations Calcium Ca+2 Magnesium Mg+2 Sodium Na+ Potassium K+

Anions Bicarbonate Sulfate Chloride Nitrate

HCO3-2 SO4 ClNO3-

These get into water from contact of water with minerals. Table 2.7 in text gives some sources for most water constituents. Overhead from Manahan. Important trace elements in nature. ANALYSES OF IONIC SPECIES Cations - atomic absorption spectrometry, atomic emission spectroscopy sample is atomized (many methods: flame, plasma arc) light beam passed through sample at wavelength specific for the compound detector measures the amount of light absorbed or emitted this is directly proportional to the concentration of the compound the limitations are: some other metals may interfere results at high concentrations are not good Anions Bicarbonate titrate with H2SO4 or HCl Sulfate gravimetric add barium chloride, barium sulfate will form and is very insoluble so it will precipitate out. Ion chromatography ion exchange column used to separate ions. Different ions have different affinities for the ion exchange resins therefore they will be separated over the length of the column.

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Flow Column
xo x xx xo ox o

Separated Sample x o xx o x x o x x After some time

sample

Initial

detection by measuring suppression of eluent conductivity. The eluent, liquid running through the column constantly, has a constant conductivity, the presence of compounds from the sample decreases the conductivity proportional to the concentration of the compound Detector Response

1st cmpd

2nd cmpd

Chloride - can use ion chromatography there are also chloride selective probes that measure the presence of the chloride ion. Similar in operation to a pH meter. Nitrate - can use a nitrate selective electrode - can use ion chromatography - can use a colorimetric reaction where you add some reagents and a color forms, the intensity of the color is directly proportional to the concentration of nitrate. The color intensity is read on a spectrophotometer. Once you have analyzed all of your samples you need to check and see if you missed anything. For a solution with electroneutrality i.e. not carrying a charge, the summation of the cations should be equal to the summation of the anions. In examining water sample there may be some error involved so an equation has been developed that can tell you if you have a complete water sample within the bounds of error usually found. This equation is: . anions cations (01065 + 0.0155 anions)

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Application (from text example 2.3 p 71) Results Cation Ca+2 Mg+2 Na+ K+ Method (1) mg/L 93.8 28 13.7 30.2 Anion HCO3SO4-2 Clmg/L 164.7 134 92.5

Prepare cation/anion balance (a) must determine mg/meq = g/eq atomic mass = eq 40.0 g/mole 2 eq/mole = 20.0 g/eq = 20.0 mg/meq

for Ca+2

(b) then divide mg/L by mg/meq for Ca+2 93.8 mg/L 20.0 mg/meq (c) total anions and cations Table Cation Ca+2 Mg+2 Na+ K+ Total mg/L 93.8 28 13.7 30.2 mg/meq 20.0 12.2 23.0 39.1 meq/L 4.69 2.3 0.6 0.77 8.36 Anion HCO3SO4-2 Clmg/L 164.7 134 92.5 mg/meq 61 48 35.5 meq/L 2.74 2.79 2.61 _____ 8.14 = 4.69 meq/L

Check for accuracy 8.14 8. 36 0.1065 + 0. 0155(8.14 ) 0.22 0.2327 This is true so the analysis is acceptable.

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In your homework you might be asked to find the missing constituents, the ?'s. To do this you must work backwards, total up one column and then fill in the missing parts of the other column and work backwards to get the missing concentrations. Be careful of units and you will have no trouble. Significance The ability to determine the constituents of a water through chemical analyses and to perform a water balance to show that the analysis is complete is the first step in determining if the water is suitable for use. Some of the constituents listed above are important as buffers, nutrients or may be toxic (nitrate is toxic to newborn children). Thus it is important to know what is in the water. Read text p. 72 (minor ionic species and non-ionic species) INORGANIC POLLUTANTS. (overhead) Of the inorganic pollutants the heavy metals (Pb, Cd, Cu, HG) and the metalloids (As, Se, Sb (Antimony)) are the most commonly found and heavily regulated. These compounds are considered toxic at low concentrations. These pollutants can be present in soluble, insoluble and organic forms. The solubility of each of the metals will depend on the pH, the redox potential, and the presence of complexing ions in the environment that they are exposed to. General Effects of Metals and metalloids -some heavy metals bind to the sulfur groups in enzymes rendering them inoperative - can also bind to carboxyl and amino groups in proteins - can bind to cell membranes, blocking transport of nutrients - can inhibit respiration and cause death - can cause neurological damage - can cause birth defects General Sources of Metals and Metalloids -Cd - mining, metal plating, -Pb - industrial, mining, batteries, leaded gasoline -Hg - batteries, lab chemicals, thermometers, fungicides, dentistry, pharmaceuticals - As - from burning of fossil fuels, from pesticides, mine tailings Each metal or metalloid has a large body of information in the literature specific to that metal. Lead. Lead gets into the environment through industrial activity especially from battery recycling and leaded gasoline. Lead was also used in paint and as pipes for plumbing. Once the hazardous nature of lead was recognized its use has been severely regulated.

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Acute lead poisoning in humans causes kidney dysfunction, reproductive system problems, and dysfunction of the liver brain and nervous system. It is also believed that lead exposure has caused mental retardation in many children. Mild lead poisoning causes anemia, headaches, sore muscles, fatigue and irritability. There is a small risk of lead exposure from drinking water if lead solder was used, but this can be minimized be running the water a bit before use. Lead is usually present in the aqueous environment in the Pb+2 form and will form insoluble complexes with almost any anion present (OVERHEAD). The biological effects of lead are believed to be dependent on the bioavailability of the lead. If the lead is present in a form that is not soluble, then it will have a minimal effect. The forms of lead that predominate in the environment are also dependent on the pH. At alkaline pHs lead is present as carbonate, oxide or hydroxide salts and usually not soluble. At acidic pHs lead may be present as the free ion, thus will have a larger biological effects.(OVERHEAD) pH pX diagram Lead can also be present as an organometallic compound. The most commonly known form is tetraethyl lead which is the form of lead used in leaded gasoline. This form is a lot more biologically active and is quite toxic. Thankfully, the organic form is not stable and will undergo chemical processes which can be catalyzed by bacteria or sunlight. These reactions release the ethyl groups from the lead one at a time. The ultimate fate of the lead from leaded gasoline is to end up as PbO in the soil. Other organic metal forms The most prominent organometal pollutants are tetraethyl lead in leaded gasoline, methyl mercury compounds, methyl arsenates, and tributyl tin compounds. Organomercury and arsenic compounds are formed as a result of microbial metabolism in the environment. This is due to the reaction between the coenzyme methyl cobalamin with the metal species e.g. HgCl 2 CH 3 HgCl + Cl or H 3 AsO 3 CH 3 AsO(OH) 2

The methyl group comes from the methylcobalamin and the methylated species can further react to form dimethyl and trimethyl species. These compounds are more biologically active than the ionic parent molecules and will accumulate in organic tissue, especially in fish tissues. The organotin compounds such as tributyl tin are very common for commercial use. The major use is as industrial biocides but they are becoming increasingly more regulated as the effects of these compounds on the environment are determined. For example the ship industry used TBT compounds to coat the hulls of ships to prevent growth of biofilms and the resultant barnacles. This use has been banned in most American harbors due to the bioaccumulation of tin in sensitive biological species.

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NUTRIENTS of importance because they will stimulate biological growth to concentrations that are more than the environment can handle. this causes detrimental effects Two problem causing nutrients 1) Nitrogen 2) Phosphorous 1) Nitrogen is added to the environment as fertilizer for agriculture and as a product of wastewater treatment Important Forms NH3 ammonia NO2 nitrite NO3 nitrate CO(NH2)2 urea N2 nitrogen gas N2 NH4+ NO2-

R-NH2

NO2-

NO3Phosphorous used for corrosion control in water synthetic detergents compounds in book p.74

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RADIOACTIVITY many natural waters have low levels of naturally occurring radioactive materials (NORMS) this is a big problem in the oil industry also in drinking water treatment The waters are brought up from the subsurface during drilling or water treatment then the radioactive materials either precipitate out in production pits or are removed during water treatment, the problem is that once brought up, they are the responsibility of the people that brought them up, this leaves concentrated radioactive waste to be disposed of and there is no method that can destroy these, they used to pump them back into the ground, but this practice is now being frowned on. Dr. Clifford, here in this program is working on a way to trap these in the underground so they are never pumped up. ALKALINITY (A) capacity of water to neutralize acid measured by titrating with a strong acid to a pH value near pH 4.5 (solution of pure CO2) or H2CO3* in this case. A = eq/m3 = [H2CO3-] + 2[CO3-2] + [OH-] - [H+] Steps to solve alkalinity problems. 1. you need to know [H2CO3-], 2[CO3-2], [OH-]. 2. convert to equivalents (watch CO3-2) 3. Add them up If results are given in equivalents then skip step 1 and 2. We very often ignore [OH-] when pH's are in the neutral range because this will be somewhere near 10-7 M so probably will not contribute. Significance Alkalinity serves as a measure of the buffering power of the water (due to carbonates) CONDUCTIVITY (EC) measures the ability of that solution to conduct an electrical current. Units are microsiemens per cm (S/cm) EC i (Ci x fi) EC = electrical conductivity Ci = concentration of ionic species in solution (meq/L) fi = conductivity factor (table 2.11) 32

IONIC STRENGTH ( ) = 1.6x10-5 EC HARDNESS Necessary to determine the effect of metal ions on water quality React with soap to form scum Cause scaling in hot water pipes, water heaters and appliances. units = eq/m3 Equated to (Ca+2) + (Mg+2) often expressed in terms of equivalent grams of CaCO3/m3 Two general types 1) carbonate hardness HCO3- and CO3-2 associated 2) non carbonate Cl- and SO4- usually 1) carbonate hardness leads to scaling upon temperature increase Ca+2 + 2HCO3- CaCO3 + CO3 + H2O H CaCO3 = scale (white crusty stuff) scaling plugs pipes, decreases heat transfer coefficients, changes frictional resistance to flow. e.g. Sample from book (Example 2.7 p 93) Species eq/m3 Ca+2 5 Mg+2 1 HCO3 3 Cl 2 Total Hardness (TH)= (Ca+2) + (Mg+2) = 5 + 1 = 6 eq/m3 Carbonate hardness (CH) = (HCO3-) = 3 eq/m3 Non carbonate hardness (NCH) = TH - CH = 6 - 3 = 3 eq/m3 Significance Hardness serves as a measure of the tendency of a water to produce scale, or other precipitates, also indicates how the water will react with soaps or detergents.

This is it for the quick survey of inorganic constituents of water. Now we must start to learn about the chemical reactions and equilibrium conditions that exist in water samples.

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Water Equilibrium and the Concept of pH There is an equilibrium that exists within the water molecule itself. This is due to the nature of the O-H bond. In water there are two O-H bonds. One of these is a true covalent bond while the other is a much weaker, ionizable bond. One hydrogen will donate its outer shell electron to the Oxygen atom thus becoming positively charged, the OH that is left will become negatively charged. You can determine the amount this will happen by examining the equilibrium of these compounds in water. =K H 2O The concentration of H2O is taken as a constant so is incorporated into K and K is then denoted as Kw therefore Kw = [H+] [OH-] if you consider a solution of pure water it should be electroneutral therefore [H+] = [OH-] we can then substitute H+ for OH- and then we get [H+]2 = Kw pH pH represents the negative log of the hydrogen concentration of water. therefore pH = -log [H+] = log 1 . = 1/2 pKw (from above). + [H ] Kw at 25C = 1 x 10-14 therefore pH = 1/2 (log 10-14) = 7 Table 2.8 has equilibrium constants for water. Significance The hydrogen ion concentration in a water has a large effect on the solubility and amounts of other constituents found in water. The pH also determines whether biological organisms can survive. The range of pH 6-8 is often used as the range in which most life can be found. There are exceptions however, some bacteria grow best at pH 2. Acids and bases Acid - substance having a tendency to donate a proton Base - substance having a tendency to accept a proton (H+ is called a proton) Equilibrium HAH+ + AH + OH -

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HA is the acid and A- is the conjugate base. Ka = the constant for the reaction going towards the release of H+ Kb = the constant for the reaction going towards the acceptance of H+ e.g. NH4+ NH3 + H+ NH4+ + OH- NH3 + H2O to balance charges

can also be written

Strong Acids and Bases Some compounds give up or accept protons very readily, these are called strong acids or bases and are said to be completely dissociated in water, this means the equilibrium goes toward the release of the proton. e.g. Ka >1 Calculations involving strong acids and bases are easy since the amount of H+ they release into water or take from water is equal to their normality. In all cases the [H+] from water can be ignored (except when you have very low concentrations (10-7). example A tank (50L) of concentrated (12M) sulfuric acid (H2SO4) is spilled into a lake with a volume of 10,000 m3. What will the pH in the lake be. Answer assumptions complete mixing has occurred. no other interfering compounds 1. amount of H+ spilled 50 L x 12 M = 600 moles 2. new concentration 600 moles 1 m3 x = 0.00006 M 1,000 L 10,000 m3 3. Since this acid dissociates completely the equilibrium is: 2 H + SO -2 4 H 2 SO 4 then the [H+] = 2 [H2SO4] = 0.00012 M pH (-log [H+]) = -log 0.00012 M = 3.92

Thus the pH of the lake after the acid spill would be 3.92 For a strong base you would use the same approach except you figure the hydroxide concentration. To get pH from this you can either figure the pOH (-log [OH-]) then subtract from 14 to get pH

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pH + pOH = 14 Weak Acids and Bases Weak acids and bases do not dissociate in water completely Ka <<1. Therefore to figure the [H+] you must use the equilibrium constant for that base. The text goes through these calculations and also takes into account the contributions from water, this gets very complicated and is not usually important. Water is a very weak acid so if you ignore it you are not introducing much error error < 5% if Ka > 10-8 example determine the pH of a 10-3 M solution of HA. Ka = 1.78 x 10-5 Ka = H+ AHA = 1.78 x 10-5

[H+] = [A-] [HA] = initial - the amount dissociated therefore 1.78 x10-5 = [ H + ][ H + ] [ H + ]2 = -3 HA [H + ] 10 [ H + ]

rearrange [H+]2 + 1.78 x 10-5 [H+] - 1.78 x 10-8 = 0 you should recognize this as a quadratic equation and be able to solve it and get [H+] = 1.25 x 10-4 Remember for your tests [H+ ] = -K a K 2 + 4 K a HA a 2 pH = 3.9

Log concentration vs. pH diagrams useful to determine probable pH when concentration of one species is known, also to find which species will be present when pH is known it only works when you have the appropriate diagram (temp, total concentration etc.) You can figure out how to draw these diagrams but it will not be necessary for this course. This will be taught to you in other courses.

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Calculations to determine concentrations of species at a given pH. Single acid base system: HA H + A+

Ka =

H + AHA

Let HA = the fraction of the total concentration of [HA] + [A-] [ HA] then HA = [ HA] + A

[ ]

from equilibrium formula we can say [HA] = [H+] [A-]/Ka

[H ][A ] K substitute this in we have HA = ([H ][A ] K ) [A ]

+ a + a

multiply by Ka/[A-] we get: HA = Therefore HA depends only on pH.

H+ H + + Ka

Total concentration of the acid = CHA = [HA] + [A-] rewrite HA = HA HA + A to be HA = [HA]/CHA

therefore

[HA] = HA x CHA

We can similarly let A- represent fraction present as the base then A

-

[A ] = =
-

C HA

[A ] = K [ HA ] + [A ] [H ] + K
a +

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Example calculate HA and A- in solution having a total = 0.1M and pH of 3. The Ka is 1.9 x 10-5. HA = H+ H + + Ka = 1x10 -3 M = 0. 98 1x10 -3 M + 1.9x10 -5

[HA] =HA x CHA = (0.98)(0.1M) = 0.098M

A- =

Ka H + + Ka

1. 9 x10 -5 = 0. 019 1x10 -3 M + 1. 9 x10 5

[A-] = A- CHA = (0.019)(0.1M) = 1.9 x 10-3 M = 0.002 M or you can calculate the first one then subtract it from the total to get the other. e.g. 0.1 M - 0.098 M = 0.002 M Polyprotic Acids e.g. H2A HA- + H+ A- + H+ K1 K2 Carbonate most important acid-base system in water controls the pH of most natural waters Equilibrium CO2 (g) CO2 (aq) + H2O H2CO3 HCO3- + H+ CO3-2 + H+ KH Km K1 K2 equilibrium of dissolved CO2 in waters exposed to the atmosphere is important. Henry's Law is applicable xCO2 = mole fraction of CO2 at equilibrium KH = Henry's law constant PCO2 = partial pressure of CO2 in atmosphere xCO2 = KH PCO2 PCO2 = 0.03% = 0.003 atm. (0.03/101.4)

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Solve the equation for 25C xCO2 = 6.11x10-4 atm-1 (0.003 atm) = 1.84 x 10-7 to determine the concentration CO 2 aq CO 2 aq CO 2 aq xCO 2 = H 2 O + CO 2 H2O 55. 56 M [CO2]aq = (1.84 x 10-7 M)(55.56 M) = 1.02 x 10-5M

Next Reaction CO2 (aq) + H2O H2CO3

[H 2CO3 ] = K = 1.58x10 3 M [CO 2 ]aq m

so [H2CO3] = Km [CO2] aq

at 25o C

= (1.58 x 10-3 M) x (1.02 x 10-5M) = 1.61 x 10-8 M This is very insignificant amount and when compared to the amount of CO2 aq and we can see that the CO2 will dominate the equilibrium. In order to calculate the rest of the equilibria we use H2CO3* to indicate that we are considering H2CO3 and CO2 aq as one thing. H2CO3* = H2CO3 + CO2 aq = 1.61 x 10-8 M+ 1.02 x 10-5 M = 1.02 x 10-5 M Next reaction using H2CO3* H2CO3* H+ + HCO3-

[H ][HCO ] = K [H CO ]
+ 3 2 * 3

= 4.47 x10 7 M at 25o C

Again we assume that [H+] = [HCO3*] Therefore 39

K1

[H ][H ] = [H CO ] [H ] = K [H CO ] . = (4.47x10 M )(102 x10

+ + 2 3 + 1 2 3 -7

= 2.13x10 -6 M pH = 5.67 This assumes that the contribution from [CO3-2] is negligible which it will be at low pH's With a K2 value of 10-11 the majority will be HCO- unless the pH is up near 11. In natural groundwater and some surface waters then we must also take into account that the water may come into contact with a solid source of carbonate such as CaCO3. rxn CaCO3 Ca+2 + CO3-2 [Ca+2] [CO3-2] = Ksp The solid form is assumed to be a constant at a concentration of 1 so it is left out of the equation. The Ksp is dependent only on the solubility and not on the amount of solid, unless the solubility is not exceeded therefore you don't get saturation and can't reach equilibrium.

Therefore we have four types of systems we may encounter in the environment 1) open system - exposed to atmosphere, gas liquid interface, no solid 2) closed system - no gas, no excess solid 3) closed system - no gas but with a solid source of carbonate 4) open system - exposed to gas and solid 1) open - such as we have been looking at. Gas liquid equilibrium must be satisfied. [H2CO3*] = 1.02x10-5 regardless of pH and at normal atmosphere etc. Figure 2.11 in text p. 87 (OVERHEAD)

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2) closed system without a source of carbonate = total carbonate = [H2CO3*] + [HCO3-] + [CO3-2] working through this the same as we have done previously (by assuming [H+] = [A-] and substituting around we will arrive at the following equations. CT

[H CO ] =
2 3 3

[H ]([H ] + K ) + K K K C [H ] HCO ] = [ [H ]([H ] + K ) + K K C [CO ] = H HK K K + K K [ ]([ ] + )

+ + 1 1 + 1 T + + 1 1 2 -2 3 1 2 T + + 1 1 2

CT H +

[ ]

3) Closed system with a source of carbonate. controlled by solid liquid equilibrium for water in contact with solid CaCO3 the value of CO3-2 is constant and can be computed using the equilibrium for dissolution of the solid rxn CaCO3 Ca+2 + CO3-2 [Ca+2] [CO3-2] = Ksp or rearranging we can see that [CO3-2] = Ksp / [Ca+2] the rest of the equations can then be determined as was done before: [CO3-2] = 4.57x10-9/[Ca+2] HCO =
3 3

4.57 x10-9 H + Ca +2 K 2 4.57 x10-9 H + K1K 2 Ca +2

2

H 2 CO =

Therefore if you know Ca+2 and pH you can determine the concentrations of any of these. Also you can see that adding Ca+2 will decrease the concentrations of all 3 of the forms. changing the pH will also alter these concentrations.

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In your homework you are asked to calculate the pH of a water sample knowing at least one of the carbonate species. To do this you will need to use the equation for the equilibrium that that species is involved in. Or you are asked to calculate the missing carbonate species knowing the pH. This is done using the equations above. Be careful which system you choose. Most samples in the lab are taken as water samples and no solid source is present. Changing the temperature can allow the solid to precipitate out and this will become a solid source. I will try and give you clear instruction as to what type of system we are dealing with in my questions but in the real world you will have to figure this out for yourself.

Significance The presence carbonate species is the major factor controlling the pH of natural waters. Carbonates also serve as a nutrient source for certain microbiological organisms. REMOVAL OF INORGANIC CONSTITUENTS Major ionic species in water The removal of major ionic species can be accomplished using a few of the treatment processes we have discussed. Ion exchange can be used to remove almost any ionic species in water. The main information needed to choose the ion exchange medium is its selectivity. Common resins are commercially available for removal of the major ions in water, (Ca+2, Mg+2, NO3-, SO42 etc.) For industrial purposes, in many cases, special resins are used with selectivity designed for the ions specific to that water. For some ions, there are other methods that are commonly used as well as ion exchange. Hardness ions - these may also be removed through precipitation with lime and soda ash. The carbonate added in the form of lime is used to convert the hardness ions to CaCO3 and Mg(OH)2 which are insoluble forms of these ions. The precipitate is then removed through coagulation and settling. The excess carbonate is removed by carbonation with CO2 gas which adjusts the pH down to more normal values. Iron and Manganese - these ions are often removed through oxidation and precipitation. (p. 583 text) air is bubbled through the water in order to oxidize the iron and manganese present. The oxidized form of the metals are less soluble and thus will precipitate out. A typical flow sheet for the removal of iron and manganese is presented in figure 11.1, p. 451 text.

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