5 FUNDAMENTALS OF CHEMICAL REACTIONS PROBLEM 5-1 Problem Statement - See text, page 343. Solution 1. Balance the reaction a. Balance alum on the right with alum on the left, There are 2 Alon the left, so increase to 2 on the right There are 3 SO on the left, so increase to 3 on the right Ala(SQg)3 18H20 + Ca(HCO3)p a3CaSO, #2AKOH)s +CO2+H,0 b. The calcium sulfate on the right was increased in step a to balance sulfate, so now balance the calcium on the left with the calcium on the right. This increases the calcium bicarbonate to 3. Alg(SQq)3 - 18H20 + 3Ca(HCO3}z = 3CaSO, + ZAIOH)3 +CO2 +H2O c._ The carbon on the left was increased in step b to balance calcium, so now balance the carbon on the right with the carbon on the left. This increases the carbon dioxide to 6. 3Ca(HCO5)}2 <2 3Ca+6HCO, 3Ca+6HCO, =? 3Ca + 60H +6CO2 The oxygen associated with Al(OH), and CO2 and the hydrogen in AN(OH)3 are balanced with the oxygen and hydrogen in Ca(HCOs)2, Alp(SO,q)3-18H,0 + SCaHCOs)p = CASO, + ZAKOH)g + SCO + HO d. The waters that are bound to the alum disassociate as HO. The final balanced equation follows. PAsSQulgrtBHg04 SCatHCOs)p eESCASO, +2AKOH +6002 +18H20 2. Compute the amount of alkalinity consumed. a. Write the chemical equation and note the molecular weight of the reactants and products involved in the reaction ot(Chapter § Fundamentals of Chemical Reactions Alg(SO4)3 1820+ 3Ca(HCO3)y 2 3CASO, + 2AI(OH)3 4 6CO2 + 18H 0 342 18x18 3x 162 3x136 2x78 8x44 18x18 b. Determine the molar relationship for the disappearance of Ca(HCOs)2 and formation of CaSO, and Al(OH}s Amountof f sucatico,, | (ose git Ca(HCo. alkalinity =| Oa)al| consumed |1MA\(S0,), 18H,0| | 1M Ca(HCO,), [_1MAL(SO,),18H,0 | [666 git Al,(SO,), 18 H,0]/ [g/t Catto, ,] [git Ai,(S0,), 18 1,0] Therefore, for 1 g/L of Alp(SO,)3 12 I iy. 7 Ca(HCO3)2, will be consumed. 34 46 (000\ 2 a9e aft Jabn PROBLEM 5-2 — Problem Statement - See text, page 343 Solution 1. Balance the reaction ‘There are 6 carbons on the right, so there must be 6 carbons on the left There are 12 hydrogens on the right, $0 there must be 12 on the left. There are now 18 oxygens on the right, $0 to balance the oxygens, add 6 to the left. The balanced reaction follows. 6002 +6H,0 > CeHy20s + 602 2. Caloulate the mg of oxygen formed per mg of CO2 removed Write the chemical equation and note the molecular weight of the reactants and products involved in the reaction CO, + 6H,0 -> CglHy205 + 602 6x44 6x18 180 6x32 The molar telationship can be determined from the above balanced reactionChapter 5 Fundamentals of Chemical Reections According to the definition of pH (pH = -log{H"}), at pH = 7, {H"}= fey tH} 107M (Hr ]= i 1M, [a] =? = agp 08 107m PROBLEM 5-6 ~ I. Instructors note: The equilibrium constant (K,) is used in this problem. The ‘equilibrium constant is also known as an acid dissociation constant and is typically reported as K, (or pKa), which is the nomenclature used here. In the dilute aqueous solutions normally encountered in water treatment, activity coefficients (j;) are assumed to be equal to 1. As the yj approaches 1, activity (fi) approaches the molar concentration ([i). Therefore, in dilute solutions, pH equals the negative log of the hydrogen ion concentration (pH = -log(H"). Problem Statement - See text, page 344 Solution 1. Calculate K, using Eq. 5-36 PK, =-l0g9K, K, = 10" = 107 2 Write the equilibrium relationship (see Eq, 5-33). (HEINE [NHS] =19928 3. Determine the ratio of [NHs] to [NH,*] at the specified pH values. a. AtpH= 6.0, the hydrogen ion concentration (H"] is equal to 10°6 and the equilibrium relationship is written as follows: (1OF}INHS) _ 49,925. INH] (Niel “INH 10°97 66a b, AtpH=7.0, the hydrogen concentration (H"] is equal to 10*7 and the equilibrium relationship is written as follows 55Chapter 5 Fundamentals of Chemical Reactions [O-"]INHg) 92s, INS) INH3] INH3] 0°25 56004073 ¢. AtpH = 8.0, the hydrogen concentration [H'] is equal to 108 and the equilibrium relationship is written as follows: (1O*]INH3] _ 49,925, INH3] _ 4g 125 562.1078 (NAG) “INHE] d. AtpH = 9.0, the hydrogen concentration [H"] is equal to 10-9 and the equilibrium relationship is written as follows’ (H0°9JINH3} _j9,925. INHa] _yo-025 _ IHG] *INHG] - e, At pH = 10, the hydrogen concentration (H"] is equal to 10"19 and the equilibrium relationship is written as follows: (10 1S]INHs] 59.928. INH3] _ 49075 oS = 107; 3 = 108 5.62 INHG) (NHG] PROBLEM 5-7 - a Problem Statement - See text, page 344 Solution 1 Convert the concentration of Fe* to molar concentration [Fe ]= (6.58 mg/L). (19/1000 mg}. (1 mole Fe* /55.8 g Fe*) =10* mole/L Determine the concentration of OH At pH = 6, the hydrogen concentration [H"] is equal to 10° cou] 10°" 10" ong al or 7 10% molest Calculate the rate of production/loss of Fe” 56|= (2.5x10")(TDS) 1 0.014 qos =! = 9.014 _ 554.53 mg/L = 554.53 25x10 25x10 ne ppm 4. Estimate EC. This drinking water can be treated as a dilute solution because ionic strength is not high, Therefore, the following relationship between TDS and EC can be used to estimate EC (see Sec. 2-4). TDS = 0.5 (EC) EC = TDSIO.5 = 554.53/0.5 = 1109 ymhofem 5. Compare the computed values to measured data. The computed TDS is 9 percent higher than the measured TDS. The estimation is reasonable comparable to measured data. The computed EC is 32.5 percent higher than measured EC, which occurs because a higher ratio of TDS to EC exists in practice than was used in the estimation. The ratio of TDS to EC for the measured data is approximately 0.6, which falls between 0.5 and 0.9. Therefore, each water sample should be characterized separately PROBLEM 5-11 Problem Statement - Plot the activity coefficients of Na”, Ca**, and AI” for ionic strengths from 0.001 M (very fresh water) to 0.5 M (seawater). Determine the ionic strength at which the activity coefficient corrections become important (activity coefficient less than 0.95) for monovalent, divalent, and trivalent ions. Solution 1. Calculate the activity coefficient for ionic strengths less than 0.005 M at 25°C using the DeBye-Hiickel limiting law (Eq. 5-42). For example, at | = 0.001 M: a. For Na’: {00,0 Yu: = —0-51(1)?V0.001 =-1.61x10? +. ,,. = 0.96 b. For Ca: 10,9 Yeqe- =-0.51(2)? VO.001 = -6.45x107 86 ‘Homework Solution Manual Page 13 0f33 MWH's Water Treatment Principles and Design, rd ed. Version 1 ‘Chapter 5 - Principles of Chemical Reactionsc. ForAl™. logo 7, = 0.513)? ¥0.001 =-0.14 Le Yyge = 0.72 2. Calculate the activity coefficient for ionic strengths less than 0.5 M at 25°C using the Davies equation (Eq. 5-43). For example, at | = 0.1 M: a. For Na’: - lod, ost vor -03x0.1] Tye = 0.78 allel (4+ V0.4 } b. For Ca** 109s Ye Yous = 0.37 ce. For Ale: 04 ) log.oy,:. =— 0.513)? -0.3x0.1|=-0.96 =011 i Yt - (Sh 3. Tabulate and plot the activity coefficients. Nee ee any an Tonic Strength Na Ca Ai 88 0.0025 0.94 079 ose 001 0.90 0.48 0.39 0.025 088 0.88 0.28 0.05 082 0.45 oar 0.078 0.80 0.40 013 oa o78 0.37 on 0.25 ora 0.30 0.07 08 073 0.29 0.08 di aes 0.3 a ae ( { = = O73 “fl (esa) ee) Homework Soliton Manual Page 140F35 MivhTs Water Treatment Principles and Design, 3d ed ‘version 1 Chapter §- Principles of Chemical Reactons1.20 ————— —+= monovalent ions) 1.00 = divalent ions | 1 trivalent ions 0.80 0.60 040 0.20 0.00 0 o4 02 03 04 05 06 lonic strength, M 4. Determine the ionic strength where the activity coefficient corrections become important. a. For monovalent ions: log,9(0.95) = - 0.541)? VI 91x10? M b. For divalent ions: log,.(0.95) = -0.5%2)?Vi 1.19%104 M c. For trivalent ions l0g,9(0.95) = -0.5%3)°Vi 2.36x10% M PROBLEM 5-12 Problem Statement - The temperature dependence of the reaction rate is frequently expressed quantitatively using parameters other than E, For example, the following expression for the reaction rate constant for the BOD test is often used ky, =kpo() 22 where T= temperature, K Homework Solution Manual Page 150138 'MUVH's Weter Treatment: Principles and Design, 3d ed, ‘Version 1 Chapter S- Principles of Chemical ReactionsPROBLEM 5-16 Problem Statement - Using a linear free-energy relationship (LFER), write an expression that could be used to estimate the reaction rate constant, kj, for the following reaction: NH,CI+HA—5 NH,CI* +47 Outline a procedure that could be used to estimate the reaction rate constant using the expression. Solution 1. Write an expression using a LFER relationship. Equation 5-90 can be used to estimate the reaction rate constant. log(k.,/N,,) = C,[PK,, +!09(N,./No,) ]+C2 2. Outline a procedure to estimate the rate constant using the above expression. a Measure the rate constants of the reactions in the problem statement for several acid species with known pK,s. List the number of exchangeable protons, Np; and maximum number of protons with which the conjugate base could combine, Na, for each species. Plot log(k,,/Np,) versus pK,, +log(Np,/Na,) Determine constants C; (slope of the curve) and C2 (intercept) using linear regression. Estimate the rate constant k; for other species using the constants determined PROBLEM 5-17 Instructors Note: This problem is similar to Example 5-9. Problem Statement - Construct plots of (a) the log concentration and (b) the percent distribution of HzCO3, HCOs, and CO? as a function of pH at Homework Solution Manual Page 21 of33 IMUVH's Water Treatmant. Principles and Dasign, rd ed Version 1 Chapter 5 - Principles of Chemical Reactons25° C. Consider a pH range of 0 to 14. Use a C100; value of 10 and assume the system is closed to the atmosphere and that the following reactions apply: H,CO; @ HCO, +H" pK; =6.35 HCO; CO," +H* pK) =10.33 Solution 1. Derive the concentration of each carbonate species in terms of C,.o, as a function of pH. a. Write the equilibrium relationship between H,CO, and HCO,” in terms of HCO, ‘for the reaction provided in the problem statement. [H' ][Hco, j_10 HCO,” ] to0,y= Eee oT) rt H00,] b. Write the equilibrium relationship between HCO,” and CO,” in terms of HCO,” for the reaction provided in the problem statement. cor HCO, ] 10°%#[HCO,”] ¢. Write the concentration of HCO,” in terms of Coo, , and then substitute this [co.*] 10": HCO," ] value into the equilbrium expressions determined in step 1a and 1 b. Creo, =[HCO,]+[HCO,”]+[Co. = 10%" HCO,” ]+[HCO,” ]+10"""* HCO,” ] = (10°F 444-10" HCO,” ] c. HCO, ]=—— 1 (HO, = par [H:00,] =o $1410 Homework Solution Manual Page 22 of 33 MWE's Water Treatment. Principles and Design, 3d ed. Version 1 Chapter 5 - Principles of Chemical Reactions2. Calculate the log concentration of each carbonate species. For example, at pH = & fuco-1- 10°M 4 “fo [Hco, ao 9.73x10“M — log[ HCO, ]=-3.01 10° Mx108* (H.00,]=sporpey apres =2-18x10"M — log[H,CO,]=~4.66 Too ]2 10M x10 a 8 104 zy [00,"]= ose a, igpws =488x10°M —log(CO,*] =-5.31 Calculate for other pH values by following the same procedure. 3. Calculate the percent of distribution. For example, at pH=8: HCO,” 40" percent or ico, = HOO], 00% = 87310°M, 100% «97 3% "1.60, 10°M percent of H,co, 2°], 1000 = EAM 100% =2.18% [co,*] 4.88x10°M it of CO,” * 100% =~ « 100% = 0.49% pereent of CO,” =4— 00% = Calculate for other pH values by following the same procedure. 4. Construct plots. a. Log concentration of H,CO, , HCO;, and CO? as a function of pH. 00 pn = 50 -100 -15.0 log concentration Homework Solution Manual Page 23 of 33 MWH's Water Treatmant: Principles and Dasign, 3rd ed. Version 1 Chapter 5 - Principles of Chemical Reactionsb. Percent distribution as a function of pH. 400.0, ————< ion B 400 Percent distrib 200 oo PROBLEM 5-18 Instructors Note: This problem is similar to Example 5-5. Problem Statement - Using the thermodynamic data given below, calculate the equilibrium constants and free energy of reaction for the following reaction at 10, 25, and 35° C: HCO; 2 HCO; +H* Thermodynamic data: F.HCO;-(aq) AG 4,004(ay) = 623-4 kJ/mole 698.7 ki/mole AG ~587.1kI/mole AH iraq) OKI mole AGE yr (q) = 0 Kd/mole Solution 1. Calculate the free energy of reaction at 25°C using Eq. 5-51 AGranico, = Arcos + AGE ~ AGFc0, §87.1+0~(~623.4) = 36.3 kJ/mole ‘Homework Solution Manual Page 24 of 33 WH’ Water Treatment: Principles and Dasign, 3d ed. Version 1 Chapter § - Princples of Chemical Reactions2. Caloulate AG,,,,.90, using Eq. 5-52 (assume activity coefficients are unity). a. Express the concentration of each species as molar concentration [HocI] =(5 mg/L) x(1.g/1000 mg)x(1 mole/71g Cl,) =7.04% 10" mole/L [H']=10*' =107 mole/L [0.]=(9 mg/L) (1.g/1000 mg) (1 mole/32 g O,) =2.81x10" mole/L b. Calculate AGaernoc TH To. 32 AGrnoci = AGimnoei + arin Uf fol” [HOCT] plore Jeon _ (10° M)x(107 m)x(2.81-10° uy" {Hocl] (7.04 10° m) =-17.55 AGannoe) = (43.16 kJ/mole) + (8.314%10° kJ/mole-K)x (298 K) x (-17.55) = ~86.65 kJ/mole 3. Determine if HOCI is thermodynamically stable in water at 25°C. The reaction given in the problem statement is thermodynamically favorable because AGaaucc << 0. Therefore, HOC! is not thermodynamically stable in water at 25°C PROBLEM 5-21 | Instructors Note: This problem is similar to Example 5-12. Problem Statement - Using the reactions shown below for the solubility of FeOHs(s), construct a pC-pH diagram and determine the Fe** concentration at pH values of 3,5, 7,9, and 11: Equilibrium. Reaction Constant Value Homework Solution Manual Page 28 of 33 MWH's Water Treatment: Principles and Design, 3rd ed. Version 3 Chapter 5 - Principles of Cnemical ResctonsFe(OH),(s) + 3H” = Fe + log Keo 3.2 3H20 Fe(OH)a(s) + 2H" = log Ks: 1.0 Fe(OH)** +2 H20 Fe(OH)a(s) +H” = logKsz — -2.5 Fe(OH)2" + H2O Fe(OH)x(s) = Fe(OH)” logKss 12.0 Fe(OH)s(s) + HO = log Ks -18.4 Fe(OH)s +H" Solution 1. Write the mass balance equation for Fe(II) Fe(III) = [Fe] + [Fe(OH)"] + [Fe(OH)2"] + [Fe(OH)s] + [Fe(OH).] Homework Solution Manual Replace each Fe(lll) species with its respective stability constant (K) relationship. a. The relationship for Fe® follows. Kg 1082 =F (HT etOHyste [Fe"]=10°1H'F Other species are derived using a similar procedure as follows: [FeOH™]=K,,[H'} = 10" [HF [Fe(OH);] =K,,[H"]=107*[H"] [Fe(OH),]=K,, =10°* [Fe(OH);] =K., (H'] = 1074 H") b. Substitute the stability constant expressions for each ion determined in step 2a into the mass balance equation derived in step 1 to establish an ‘expression for the total Fe(|II) concentration in terms of stability constants. Fe(Ill) = Kgg [HT + Kg, (H"F + Ko (H'] + Kg3 + Kga/IH'] Fe(Ill) = 10°? [H"}? + 10°° [H'? + 1075 [H7] + 107° + 107°7H"] Page 20 0f33 MWH's Watar Treatment. Principles end Design, rd ed Version 1 Chapter 5 - Principles of Chemical Reactions3. _ Plot the equations for each species as developed in step 2, and identify the line that represents the total Fe(II!) concentration as follows: Crea. i298 4 6 6 7 8 @& 10 41 12 45.44. 4, Determine the concentration of Fe*+ at the pH values listed in the problem ‘statement. This can be done either graphically from the plot created in'step 3 or by calculating [Fe*] using the equation developed in step 2a. The equation method follows: a pH=3 [Fe] = 10°2(10°)" =1.5810"M b. pH=5 [Fe**]=10°2(10")’ =1.58x10-"M c pH=7: [Fe*"]=10°? (107) =1.58«10""M 4. pH=9: Homework Solution Manual Page 30 of 33 MWH's Water Treatment Principles and Design, 3 ed Version 1 CChapler 5 - Principles of Chemical Reeetions[Fe*] =10°7(10" 58x10%M e pH=41: [Fe**] = 10°?(10"") = 1.58 107"M PROBLEM 65-22 Problem Statement - Manganese, Mn(Il) is soluble in water and is present in many groundwaters because insoluble forms (e.g., MnO2) that are contained in minerals are reduced to soluble forms. (The subsurface is a reducing environment, because electron acceptors such as oxygen have been used up by heterotrophic bacteria in the A horizon of soil, comprised mainly of mineral material and organic detritus ‘such as peat.) Ozone (O;) is sometimes used to remove Mn according to the reaction Mn’™* + Oyaq) +H;0 & MnOy49) + Ogg) + 2H* Compute the equilibrium constant for the reaction and plot the free energy as a function of the conversion of Mn** from 0.01 to 0.999 using the following data AG gyn =-164.05 kJ/mole Assume that the initial reactant concentrations are DO = 10 mg/L, Os = 0.5 mg/L, Mn** = 2 mg/L, and MnO; = 0 mgJlL. Solution 1. Caloulate the equilibrium constant using Eqs. 5-52 and 5-83. AGae, = AGZ,, +RTINQ At equilibrium AG,,,= 0 and Q = Keg per Eq. 6-57. “AG2, —-RTink,, Calculate the value of Ke, using Eq. 5-58. 2 er Homework Solution Manual Page 31 of33 MWH's Water Treatment, Principles and Design, 3rd eo Version 1 Chapter §- Principles of Chemical Resctions