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(a) Following the example of Mg(OH)2 in Section 8-5, write the equations needed to find the solubility of Ca(OH)2. Include activity coefficients where appropriate. Look up the equilibrium constants in Appendixes F and I.

(b) Suppose that the size of CaOH+= Ca(H2O)5(OH)+ is 500 pm. Including activity coefficients, compute the concentrations of all species, the fraction of hydrolysis (= [CaOH+]/{[Ca2+] + [CaOH+]}), and the solubility of Ca(OH)2 in g/L. The Handbook of Chemistry and Physics lists the solubility of Ca(OH)2 as 1.85 g/L at 00C and 0.77 g/L at 1000C

Short Answer

Expert verified

(a)

The equilibrium reactions are

CaOH2KspCa2++2OH----(1)Ca2++2OH-K1CaOH+----(2)H2OKwH++OH------(3)

Charge balance is written as follows

2Ca2++CaOH++H+=OH------(4)

Mass balance is written as follows

22Ca2++CaOH++H+=OH-+CaOH+----(5)

(b)

The values obtained are as follows

[Ca2+] =0.01 M, [OH-]=0.0253 M, [CaOH+]= 0.005 M, and [H+闭=3.94脳10-13M

The fraction of hydrolysis =0.333

Solubility=74.09脳0.015 g/L= 1.11 g/L

Step by step solution

01

Calculation regarding part (a)

(a)

The equilibrium reactions are

CaOH2KspCa2++2OH----(1)Ca2++2OH-K1CaOH+----(2)H2OKwH++OH------(3)

Ksp=6.510-6K1=2.0101Kw=1.010-14Ksp=Ca2+Ca2+OH-2OH-2K1=CaOH+Ca2+Ca2+OH-OH-Kw=H+H+OH-OH-

Charge balance is written as follows

2Ca2++CaOH++H+=OH------(4)

Mass balance is written as follows

22Ca2++CaOH++H+=OH-+CaOH+----(5)

02

Calculation regarding part (b)

(b)

Neglecting the activity coefficient and neglecting [H+] in the charge balance because [H+] <<[OH-] in basic solution.

Therefore, the charge balance becomes

2Ca2++CaOH+=OH-----(6)

After substituting [CaOH+] we get

2Ca2++K1Ca2+OH-=OH-Ca2+=OH-2+K1OH-Ksp=Ca2+OH-2=OH-32+K1OH-

Equation 7 must be solved using spreadsheet and by guessing the[OH-] value

Using SOLVER the following spreadsheet was obtained

The values obtained are as follows

[Ca2+] =0.01 M, [OH-]=0.0253 M, [CaOH+]= 0.005 M, and [H+闭=3.94脳10-13M

The fraction of hydrolysis =( [CaOH+]/{[Ca2+] + [CaOH+]})=0.333

Total dissolved Ca=0.01+0.005=0.015M

Formula mass of Ca(OH)2 74.09 g/mol

Solubility=74.09脳0.015 g/L= 1.11 g/L

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Most popular questions from this chapter

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Sodium acetate hydrolysis treated by Solver with activity coefficients.

(a) Following the NH3 example in Section 8-5, write the equilibria and charge and mass balances needed to find the composition of 0.01 M sodium acetate (Na+A-). Include activity coefficients where appropriate. The two reactions are hydrolysis (pKb = 9.244) and ionization of H2O.

(b) Including activity coefficients, set up a spreadsheet analogous to Figure 8-12 to find the concentrations of all species. Assign an initial value of ionic strength = 0.01. After the rest of the spreadsheet is set up, change the ionic strength from the numerical value 0.01 to the correct formula for ionic strength. This two-step process of beginning with a numerical value and then going to a formula is necessary because of circular references between ionic strength and concentrations that depend on ionic strength. There are four unknowns and two equilibria, so use Solver to find 4 - 2 = 2 concentrations (pC values). Solver does not find both pC values at the same time well in this problem. Execute one pass to find both pC values by varying pA and pOH to minimizebi2 . Then vary only pA to minimizebi2 . Then vary only pOH to minimize bi2. Continue alternating to solve for one value at a time as long as bi2 continues to decrease. Find [A-], [OH-], [HA], and [H+]. Find the ionic strength, pH =-log([H+] +) and the fraction of hydrolysis = [HA]/F.

Systematic treatment of equilibrium for ion pairing. Let鈥檚 derive the fraction of ion pairing for the salt in Box 8-1, which are 0.025FNaCI,Na2SO4,MgCI2,MgSO4. Each case is somewhat different. All of the solutions will be near neutral pH because hydrolysis reactions of Mg2+,SO2-4,Na+,CI-have small equilibrium constants. Therefore, we assume that H+=OH-and omit these species from the calculations. We work MgCI2as an example and then you asked to work each of the others. The ion-pair equilibrium constant, Kipcomes from Appendix J.

Pertinent reaction:

Mg2+CI-MgCI+aqKip=MgCI+aqMgCI+Mg2+Mg2+CI-CI-logKip=0.6.pKip=-0.6A

Charge balance (omitting H+,OH-whose concentrations are both small in comparison with Mg+,MgCI+,CI-:

role="math" localid="1655088043259" 2Mg2-+MgCI+=CI-B

Mass balance:

Mg2-+MgCI+=F=0.025MCCI-+MgCI+=2F=0.050MD

Only two of the three equations (B),(C) and (D) are independent. If you double (c) and subtract (D) , you will produce (B). we choose (C) and (D) as independent equations.

Equilibrium constant expression : Equation (A)

Count : 3 equations (A,C,D) and 3 unknowns Mg2+,MgCI+,CI-

Solve: We will use Solver to find

numberofunknowns-numberofequiliberia=3-1=2unknown concentrations.

The spreadsheet shows the work. Formal concentration F=0.0025Mappears in cell G2. We estimate pMg2+,pCI-in cell B8and B9. The ionic strength in cell B5is given by the formula in cell H24. Excel must be set to allow for circular definitions as described on page role="math" localid="1655088766279" 179. The sizes of role="math" localid="1655088853561" Mg2+,CI-are from Table 8-1and the size of MgCI+is a guess. Activity coefficient are computed in columns E,F. Mass balance b1=F-Mg2+-MGCI+,b2=2F-CI--MgCI+appears in cell H14,H15, and the sum of squares b21+b22 appears in cell H16. The charge balance is not used because it is not independentof the two mass balances.

Solver is invoked to minimizes b21+b22in cell H16be varying pMg2+,pCI-in cells B8and B9. From the optimized concentration, the ion-pair fraction =MgCI+F=0.0815is computed in cell D15.

The problem: Create a spreadsheet like the one for MgCI+to find the concentration, ionic strength, and ion pair fraction in 0.025MNaCI. The ion pair formation constant from Appendix J is log Kip=10-0.5for the reaction Na++CI-NaCIaq. The two mass balances are Na++NaCIaq=F,Na+=CI-Estimate pNa+,pCI- for input and then minimizes the sum of square of the two mass balances.

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