On increasing the volume, the same vapour occupies a larger space, so its pressure falls at once. The rate of condensation decreases because vapour molecules strike the liquid surface less frequently, while the rate of evaporation is initially almost unchanged. More liquid evaporates until equilibrium is re-established; at the same temperature the final vapour pressure again equals the original equilibrium vapour pressure.
Initially the vapour pressure decreases, evaporation is greater than condensation, and finally the same vapour pressure is restored.
For 2SO2(g) + O2(g) ⇌ 2SO3(g), Kc = [SO3]^2/([SO2]^2[O2]). Substituting the concentrations, Kc = (1.90)^2/[(0.60)^2(0.82)] = 12.23, so Kc is approximately 12.2.
Kc = 12.2.
Volume percent equals mole percent for gases. Thus pI = 0.40 x 10^5 Pa and pI2 = 0.60 x 10^5 Pa. For I2(g) ⇌ 2I(g), Kp = (pI)^2/pI2 = (4.0 x 10^4)^2/(6.0 x 10^4) = 2.67 x 10^4 Pa.
Kp = 2.67 x 10^4 Pa.
Pure solids and pure liquids are omitted from Kc because their activities are constant. Therefore only gaseous and aqueous species appear in the expressions with powers equal to their stoichiometric coefficients.
(i) Kc = [NO]^2[Cl2]/[NOCl]^2; (ii) Kc = [NO2]^4[O2]; (iii) Kc = [CH3COOH][C2H5OH]/[CH3COOC2H5]; (iv) Kc = 1/([Fe3+][OH-]^3); (v) Kc = [IF5]^2/[F2]^5.
Use Kp = Kc(RT)^Δn with R = 0.0831 L bar K^-1 mol^-1. For (i), Δn = 3 - 2 = 1, so Kc = 1.8 x 10^-2/(0.0831 x 500) = 4.33 x 10^-4. For (ii), Δn = 1, so Kc = 167/(0.0831 x 1073) = 1.87, approximately 1.90.
(i) Kc = 4.33 x 10^-4; (ii) Kc = 1.90.
The equilibrium constant for the reverse reaction is the reciprocal of that for the forward reaction. Thus Kc(reverse) = 1/(6.3 x 10^14) = 1.59 x 10^-15.
Kc for the reverse reaction = 1.59 x 10^-15.
For a pure solid or pure liquid, the amount present may change but its active mass does not change appreciably at a fixed temperature. That constant factor is absorbed into the numerical value of the equilibrium constant, so pure solids and pure liquids are omitted from K expressions.
Because their concentrations or activities remain constant at a fixed temperature.
Formation of 0.0518 mol NOBr consumes 0.0518 mol NO and 0.0518/2 = 0.0259 mol Br2 from the stoichiometry 2NO + Br2 ⇌ 2NOBr. Therefore NO left = 0.087 - 0.0518 = 0.0352 mol, and Br2 left = 0.0437 - 0.0259 = 0.0178 mol.
NO = 0.0352 mol; Br2 = 0.0178 mol.
For 2SO2(g) + O2(g) ⇌ 2SO3(g), Δn = 2 - 3 = -1. Hence Kp = Kc(RT)^-1, so Kc = KpRT = (2.0 x 10^10)(0.0831)(450) = 7.48 x 10^11.
Kc = 7.48 x 10^11.
HI pressure decreases from 0.20 atm to 0.04 atm, so 0.16 atm of HI decomposes. From 2HI ⇌ H2 + I2, pH2 = pI2 = 0.16/2 = 0.08 atm. Therefore Kp = (pH2 pI2)/(pHI)^2 = (0.08 x 0.08)/(0.04)^2 = 4.
Kp = 4.
Concentrations are [N2] = 1.57/20 = 0.0785 M, [H2] = 1.92/20 = 0.096 M and [NH3] = 8.13/20 = 0.4065 M. Qc = [NH3]^2/([N2][H2]^3) = 2.38 x 10^3. Since Qc > Kc (1.7 x 10^2), there is excess product and the reaction shifts backward to form N2 and H2.
The mixture is not at equilibrium; the net reaction proceeds in the reverse direction.
40% of 1 mol water reacts, so x = 0.40 mol. At equilibrium, H2O = CO = 0.60 mol and H2 = CO2 = 0.40 mol. Volume cancels because Δn = 0. Therefore Kc = ([H2][CO2])/([H2O][CO]) = (0.40 x 0.40)/(0.60 x 0.60) = 0.44.
Kc = 0.44.
For H2 + I2 ⇌ 2HI, Kc = [HI]^2/([H2][I2]). Starting with HI only gives equal H2 and I2 at equilibrium, say x each. Thus 54.8 = (0.5)^2/x^2, so x = sqrt(0.25/54.8) = 0.0675 M.
[H2] = [I2] = 0.0675 mol L^-1.
Let [I2] = [Cl2] = x at equilibrium. Then [ICl] = 0.78 - 2x. Kc = x^2/(0.78 - 2x)^2 = 0.14. Taking square root, x/(0.78 - 2x) = sqrt(0.14). Solving gives x = 0.167 M and [ICl] = 0.446 M.
[ICl] = 0.446 M; [I2] = [Cl2] = 0.167 M.
Let x atm of C2H6 decompose. Then pC2H4 = pH2 = x and pC2H6 = 4.0 - x. Kp = x^2/(4.0 - x) = 0.04, giving x = 0.380 atm and pC2H6 = 3.62 atm. Using p = CRT, C = 3.62/(0.0821 x 899) = 0.049 mol L^-1.
p(C2H6) = 3.62 atm, corresponding to [C2H6] = 0.049 mol L^-1 at 899 K.
Water is part of the reacting mixture, so it is included. In (ii), ester = water = 0.171 mol, acetic acid = 1.00 - 0.171 = 0.829 mol and ethanol = 0.18 - 0.171 = 0.009 mol. Kc = (0.171 x 0.171)/(0.829 x 0.009) = 3.92. In (iii), Qc = (0.214 x 0.214)/[(1.0 - 0.214)(0.5 - 0.214)] = 0.204, which is less than Kc, so equilibrium has not been reached and the forward reaction continues.
(i) Qc = [CH3COOC2H5][H2O]/([CH3COOH][C2H5OH]); (ii) Kc = 3.92; (iii) equilibrium has not been reached, and the reaction proceeds forward.
For PCl5 ⇌ PCl3 + Cl2, Kc = [PCl3][Cl2]/[PCl5]. Starting with pure PCl5 gives [PCl3] = [Cl2] = x. Thus 8.3 x 10^-3 = x^2/(0.5 x 10^-1), so x = sqrt(8.3 x 10^-3 x 0.05) = 2.04 x 10^-2 M.
[PCl3] = [Cl2] = 2.04 x 10^-2 mol L^-1.
Qc = [NH3]^2/([N2][H2]^3) = (0.5)^2/[3.0 x (2.0)^3] = 0.0104. Since Qc < Kc = 0.061, the mixture has too little product, so the reaction proceeds forward to form more NH3.
The reaction is not at equilibrium; it proceeds in the forward direction.
Let [Br2] = [Cl2] = x at equilibrium. Then [BrCl] = 3.3 x 10^-3 - 2x. Kc = x^2/(3.3 x 10^-3 - 2x)^2 = 32. Taking square root and solving gives x = 1.516 x 10^-3 M, so [BrCl] = 3.3 x 10^-3 - 2x = 2.68 x 10^-4 M.
[BrCl] = 2.68 x 10^-4 mol L^-1.
For NO(g) + 1/2 O2(g) ⇌ NO2(g), ∆rG° = ∆fG°(NO2) - [∆fG°(NO) + 1/2∆fG°(O2)] = 52.0 - 87.0 = -35.0 kJ mol^-1. From ∆G° = -RT ln K, ln K = 35000/(8.314 x 298) = 14.13. Therefore K = e^14.13 = 1.37 x 10^6.
∆G° = -35.0 kJ mol^-1; K = 1.37 x 10^6.
Decreasing pressure favours the side with more gaseous moles. In (a), products have two gas moles versus one on the reactant side, so products increase. In (b), the gaseous side is the reactant side, so products decrease. In (c), both sides have four gaseous moles, so the amount of products remains essentially unchanged.
(a) Increase; (b) decrease; (c) remain same.
Increasing pressure favours the side with fewer gaseous moles. In (i), 1 gas mole is on the reactant side and 2 on the product side, so the shift is backward. In (ii), gaseous moles are equal, so pressure has no effect. In (iii), 1 gas mole shifts backward from 2 gas moles. In (iv), 3 gas moles shift forward to 1 gas mole. In (v), the backward side has no gas. In (vi), 9 gas moles on the reactant side are favoured over 10 gas moles on the product side.
(i) backward; (ii) not affected; (iii) backward; (iv) forward; (v) backward; (vi) backward.
Starting with HBr only, let pH2 = pBr2 = x at equilibrium. Then pHBr = 10.0 - 2x. Kp = (pHBr)^2/(pH2 pBr2) = (10.0 - 2x)^2/x^2 = 1.6 x 10^5. Taking square root, (10.0 - 2x)/x = 400, so x = 10.0/402 = 0.0249 bar and pHBr = 9.95 bar.
pH2 = pBr2 = 0.0249 bar and pHBr = 9.95 bar.
For the reaction CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g), Kp is the product partial pressures divided by reactant partial pressures with stoichiometric powers. Increasing pressure favours fewer gas moles, so the equilibrium shifts to CH4 and H2O, but Kp is unchanged at fixed temperature. Since the forward reaction is endothermic, increasing temperature favours products and increases Kp. A catalyst only helps equilibrium be reached faster; it does not change Kp or the equilibrium composition.
Kp = pCO(pH2)^3/(pCH4 pH2O). Pressure increase shifts the composition backward without changing Kp; temperature increase raises Kp and favours products; catalyst does not change Kp or equilibrium composition.
By Le Chatelier's principle, adding a reactant shifts equilibrium towards product, while adding product shifts it towards reactants. Removing a reactant shifts backwards to replace it, and removing product shifts forwards to replace the product. Therefore addition of H2 and removal of CH3OH favour methanol formation, while addition of CH3OH and removal of CO favour the reverse reaction.
(a) forward shift; (b) backward shift; (c) backward shift; (d) forward shift.
For PCl5(g) ⇌ PCl3(g) + Cl2(g), Kc = [PCl3][Cl2]/[PCl5]. The reverse reaction has Kc = 1/(8.3 x 10^-3) = 1.20 x 10^2. At a fixed temperature, changing concentration or pressure may shift the equilibrium composition but does not change Kc. Since decomposition is endothermic, increasing temperature favours decomposition and increases Kc.
(a) Kc = [PCl3][Cl2]/[PCl5]; (b) 1.20 x 10^2; (c) adding PCl5 or increasing pressure does not change Kc, while increasing temperature increases Kc.
Let pH2 = pCO2 = x at equilibrium. Then pCO = pH2O = 4.0 - x. Kp = (pCO2 pH2)/(pCO pH2O) = x^2/(4.0 - x)^2 = 10.1. Taking square root, x/(4.0 - x) = sqrt(10.1). Solving gives x = 3.04 bar.
pH2 = 3.04 bar.
When Kc is extremely small, reactants dominate; when Kc is extremely large, products dominate. Reaction (a) has Kc = 5 x 10^-39, so reactants dominate. Reaction (b) has Kc = 3.7 x 10^8, so products dominate. Reaction (c) has Kc close to 1, so both reactants and products are appreciably present.
Only reaction (c) will have appreciable concentrations of both reactants and products.
Kc = [O3]^2/[O2]^3. Hence [O3] = sqrt(Kc[O2]^3) = sqrt((2.0 x 10^-50)(1.6 x 10^-2)^3) = 2.86 x 10^-28 M.
[O3] = 2.86 x 10^-28 mol L^-1.
In the 1 L flask, the given moles are numerically the molar concentrations. Kc = [CH4][H2O]/([CO][H2]^3). Therefore [CH4] = Kc[CO][H2]^3/[H2O] = (3.90)(0.30)(0.10)^3/0.02 = 0.0585 M.
[CH4] = 0.0585 mol L^-1.
A Lewis acid accepts an electron pair. BF3 accepts an electron pair because boron has an incomplete octet. H+ accepts an electron pair to form a bond. NH4+ can act as an acid through its proton. H2O has lone pairs and normally donates an electron pair, so it is a Lewis base.
BF3, H+ and NH4+ act as Lewis acids; H2O is a Lewis base.
A conjugate base is obtained when an acid loses one proton. HF loses H+ to form F-. H2SO4 loses H+ to form HSO4-. HCO3- loses H+ to form CO3^2-.
F-, HSO4- and CO3^2-, respectively.
A conjugate acid is obtained by adding one proton to a base. NH2- + H+ → NH3. NH3 + H+ → NH4+. HCOO- + H+ → HCOOH.
NH3, NH4+ and HCOOH, respectively.
For each amphiprotic species, adding H+ gives its conjugate acid and removing H+ gives its conjugate base. H2O gives H3O+ and OH-. HCO3- gives H2CO3 and CO3^2-. HSO4- gives H2SO4 and SO4^2-. NH3 gives NH4+ and NH2-.
H2O: H3O+ and OH-; HCO3-: H2CO3 and CO3^2-; HSO4-: H2SO4 and SO4^2-; NH3: NH4+ and NH2-.
OH- and F- possess lone pairs and can donate an electron pair, so they are Lewis bases. H+ accepts an electron pair from a donor to form a covalent bond, so it is a Lewis acid. BCl3 has an electron-deficient boron atom with an empty orbital and accepts an electron pair, so it is also a Lewis acid.
OH- and F- are Lewis bases; H+ and BCl3 are Lewis acids.
pH = -log[H+] = -log(3.8 x 10^-3) = 2.42.
pH = 2.42.
[H+] = 10^-pH = 10^-3.76 = 1.74 x 10^-4 M.
[H+] = 1.74 x 10^-4 M.
For a conjugate acid-base pair, KaKb = Kw = 1.0 x 10^-14 at 298 K. Therefore Kb(F-) = 10^-14/(6.8 x 10^-4) = 1.47 x 10^-11; Kb(HCOO-) = 10^-14/(1.8 x 10^-4) = 5.56 x 10^-11; Kb(CN-) = 10^-14/(4.8 x 10^-9) = 2.08 x 10^-6.
F-: 1.47 x 10^-11; HCOO-: 5.56 x 10^-11; CN-: 2.08 x 10^-6.
For phenol alone, [C6H5O-] ≈ sqrt(KaC) = sqrt((1.0 x 10^-10)(0.05)) = 2.24 x 10^-6 M. With 0.01 M sodium phenolate, [C6H5O-] is approximately 0.01 M from the salt. Ka = [H+][C6H5O-]/[C6H5OH], so [H+] = (1.0 x 10^-10)(0.05)/0.01 = 5.0 x 10^-10 M. Degree of ionization = [H+]/0.05 = 1.0 x 10^-8.
[C6H5O-] = 2.24 x 10^-6 M in pure phenol solution; degree of ionization in 0.01 M sodium phenolate = 1.0 x 10^-8.
For H2S alone, [HS-] ≈ sqrt(Ka1 C) = sqrt((9.1 x 10^-8)(0.1)) = 9.54 x 10^-5 M. For the second ionization, Ka2 = [H+][S2-]/[HS-]; since [H+] ≈ [HS-] in the weak-acid solution, [S2-] ≈ Ka2 = 1.2 x 10^-13 M. In 0.1 M HCl, [H+] ≈ 0.1 M, so [HS-] = Ka1[H2S]/[H+] = (9.1 x 10^-8)(0.1)/0.1 = 9.1 x 10^-8 M. Then [S2-] = Ka2[HS-]/[H+] = (1.2 x 10^-13)(9.1 x 10^-8)/0.1 = 1.09 x 10^-19 M.
In 0.1 M H2S: [HS-] = 9.54 x 10^-5 M and [S2-] ≈ 1.2 x 10^-13 M. In 0.1 M HCl: [HS-] = 9.1 x 10^-8 M and [S2-] = 1.09 x 10^-19 M.
For weak acetic acid, α ≈ sqrt(Ka/C) = sqrt((1.74 x 10^-5)/0.05) = 0.0187. Therefore [CH3COO-] = Cα = 0.05 x 0.0187 = 9.33 x 10^-4 M, equal to [H+]. pH = -log(9.33 x 10^-4) = 3.03.
Degree of dissociation = 0.0187; [CH3COO-] = 9.33 x 10^-4 M; pH = 3.03.
[H+] = 10^-4.15 = 7.08 x 10^-5 M, so [A-] = 7.08 x 10^-5 M. For HA ⇌ H+ + A-, Ka = [H+][A-]/[HA] = x^2/(0.01 - x) = (7.08 x 10^-5)^2/(0.009929) = 5.05 x 10^-7. pKa = -log Ka = 6.30.
[A-] = 7.08 x 10^-5 M; Ka = 5.05 x 10^-7; pKa = 6.30.
For strong acids, pH = -log[H+]. For strong bases, pOH = -log[OH-] and pH = 14 - pOH. Thus HCl: pH = -log(0.003) = 2.52. NaOH: pOH = -log(0.005) = 2.30, so pH = 11.70. HBr: pH = -log(0.002) = 2.70. KOH: pOH = -log(0.002) = 2.70, so pH = 11.30.
(a) 2.52; (b) 11.70; (c) 2.70; (d) 11.30.
(a) Molar mass of TlOH ≈ 221.4 g mol^-1; [OH-] = (2/221.4)/2 = 4.52 x 10^-3 M, pH = 11.65. (b) Moles Ca(OH)2 = 0.3/74.1 = 4.05 x 10^-3 in 0.500 L, so [OH-] = 2(4.05 x 10^-3)/0.500 = 0.0162 M and pH = 12.21. (c) [OH-] = (0.3/40.0)/0.200 = 0.0375 M, pH = 12.57. (d) [H+] = (13.6 x 0.001)/1.000 = 0.0136 M, pH = 1.87.
(a) 11.65; (b) 12.21; (c) 12.57; (d) 1.87.
[H+] = Cα = 0.1 x 0.132 = 0.0132 M, so pH = -log(0.0132) = 1.88. Ka = Cα^2/(1 - α) = 0.1(0.132)^2/(1 - 0.132) = 2.01 x 10^-3. Therefore pKa = -log(2.01 x 10^-3) = 2.70.
pH = 1.88; pKa = 2.70.
pOH = 14 - 9.95 = 4.05, so [OH-] = 10^-4.05 = 8.91 x 10^-5 M. For the weak base, [BH+] = [OH-] = x and [B] = 0.005 - x. Kb = x^2/(0.005 - x) = (8.91 x 10^-5)^2/(0.00491) = 1.62 x 10^-6. Hence pKb = -log Kb = 5.79.
Kb = 1.62 x 10^-6; pKb = 5.79.
From Table 6.7, Kb(aniline) = 4.27 x 10^-10. For 0.001 M aniline, [OH-] ≈ sqrt(KbC) = sqrt((4.27 x 10^-10)(0.001)) = 6.53 x 10^-7 M. Therefore pOH = 6.185 and pH = 7.82. Degree of ionization = [OH-]/C = 6.53 x 10^-7/0.001 = 6.53 x 10^-4. For the conjugate acid, Ka = Kw/Kb = 10^-14/(4.27 x 10^-10) = 2.34 x 10^-5.
pH = 7.82; degree of ionization = 6.53 x 10^-4; Ka of conjugate acid = 2.34 x 10^-5.
Ka = 10^-4.74 = 1.82 x 10^-5. In pure acid, α ≈ sqrt(Ka/C) = sqrt((1.82 x 10^-5)/0.05) = 0.0191. In the presence of strong acid, ionization is suppressed and α ≈ Ka/[H+]. With 0.01 M HCl, α = 1.82 x 10^-5/0.01 = 1.82 x 10^-3. With 0.1 M HCl, α = 1.82 x 10^-5/0.1 = 1.82 x 10^-4.
In pure 0.05 M acetic acid, α = 0.0191. In 0.01 M HCl, α = 1.82 x 10^-3; in 0.1 M HCl, α = 1.82 x 10^-4.
For dimethylamine, Kb = Cα^2/(1 - α). Substituting Kb = 5.4 x 10^-4 and C = 0.02 gives α = 0.151, about 15.1%. In 0.1 M NaOH, the common OH- ion suppresses ionization, and α ≈ Kb/[OH-] = (5.4 x 10^-4)/0.1 = 5.4 x 10^-3. Percentage ionized = 0.54%.
Degree of ionization in 0.02 M solution = 0.151; in 0.1 M NaOH, 0.54% is ionized.
Use [H+] = 10^-pH. Muscle fluid: 10^-6.83 = 1.48 x 10^-7 M. Stomach fluid: 10^-1.2 = 6.31 x 10^-2 M. Blood: 10^-7.38 = 4.17 x 10^-8 M. Saliva: 10^-6.4 = 3.98 x 10^-7 M.
(a) 1.48 x 10^-7 M; (b) 6.31 x 10^-2 M; (c) 4.17 x 10^-8 M; (d) 3.98 x 10^-7 M.
Use [H+] = 10^-pH. For pH 6.8, [H+] = 1.58 x 10^-7 M. For pH 5.0, [H+] = 1.0 x 10^-5 M. For pH 4.2, [H+] = 6.31 x 10^-5 M. For pH 2.2, [H+] = 6.31 x 10^-3 M. For pH 7.8, [H+] = 1.58 x 10^-8 M.
Milk: 1.58 x 10^-7 M; black coffee: 1.0 x 10^-5 M; tomato juice: 6.31 x 10^-5 M; lemon juice: 6.31 x 10^-3 M; egg white: 1.58 x 10^-8 M.
Moles of KOH = 0.561/56.1 = 0.0100 mol. Volume = 0.200 L, so [K+] = [OH-] = 0.0100/0.200 = 0.050 M. At 298 K, [H+] = Kw/[OH-] = 1.0 x 10^-14/0.050 = 2.0 x 10^-13 M. pOH = -log(0.050) = 1.30, so pH = 12.70.
[K+] = 0.050 M; [OH-] = 0.050 M; [H+] = 2.0 x 10^-13 M; pH = 12.70.
Molar mass of Sr(OH)2 = 121.6 g mol^-1. Molar solubility = 19.23/121.6 = 0.158 M, so [Sr2+] = 0.158 M. Since Sr(OH)2 gives two hydroxide ions, [OH-] = 2 x 0.158 = 0.316 M. pOH = -log(0.316) = 0.500, so pH = 13.50.
[Sr2+] = 0.158 M; [OH-] = 0.316 M; pH = 13.50.
For 0.05 M propanoic acid, α ≈ sqrt(Ka/C) = sqrt((1.32 x 10^-5)/0.05) = 0.0162. Thus [H+] = Cα = 0.05 x 0.0162 = 8.12 x 10^-4 M and pH = 3.09. In 0.01 M HCl, α ≈ Ka/[H+] = (1.32 x 10^-5)/0.01 = 1.32 x 10^-3.
In pure solution, α = 0.0162 and pH = 3.09. In 0.01 M HCl, α = 1.32 x 10^-3.
[H+] = 10^-2.34 = 4.57 x 10^-3 M. Degree of ionization α = [H+]/C = (4.57 x 10^-3)/0.1 = 0.0457. Ka = x^2/(C - x) = (4.57 x 10^-3)^2/(0.1 - 0.00457) = 2.19 x 10^-4.
Ka = 2.19 x 10^-4; degree of ionization = 0.0457.
NO2- is the conjugate base of HNO2. Kb = Kw/Ka = 1.0 x 10^-14/(4.5 x 10^-4) = 2.22 x 10^-11. For 0.04 M sodium nitrite, [OH-] ≈ sqrt(KbC) = sqrt((2.22 x 10^-11)(0.04)) = 9.43 x 10^-7 M. pOH = 6.03, so pH = 7.97. Degree of hydrolysis = [OH-]/C = 9.43 x 10^-7/0.04 = 2.36 x 10^-5.
pH = 7.97; degree of hydrolysis = 2.36 x 10^-5.
Pyridinium ion is the conjugate acid of pyridine. [H+] = 10^-3.44 = 3.63 x 10^-4 M. For 0.02 M pyridinium ion, Ka = x^2/(C - x) = (3.63 x 10^-4)^2/(0.02 - 3.63 x 10^-4) = 6.71 x 10^-6. Therefore Kb(pyridine) = Kw/Ka = 1.0 x 10^-14/(6.71 x 10^-6) = 1.49 x 10^-9.
Kb for pyridine = 1.49 x 10^-9.
Salts of strong acid and strong base are neutral, so NaCl and KBr are neutral. Salts containing anions of weak acids with strong-base cations are basic, so NaCN, NaNO2 and KF are basic. NH4NO3 contains NH4+, the conjugate acid of weak base NH3, and NO3- from a strong acid, so its solution is acidic.
NaCl and KBr are neutral; NaCN, NaNO2 and KF are basic; NH4NO3 is acidic.
For the acid, solve Ka = x^2/(0.1 - x) with Ka = 1.35 x 10^-3. This gives [H+] = x = 1.10 x 10^-2 M and pH = 1.96. For the sodium salt, Kb = Kw/Ka = 7.41 x 10^-12. [OH-] ≈ sqrt(KbC) = sqrt((7.41 x 10^-12)(0.1)) = 8.61 x 10^-7 M. pOH = 6.07, so pH = 7.93.
pH of 0.1 M chloroacetic acid = 1.96; pH of 0.1 M sodium chloroacetate = 7.93.
For neutral water, [H+] = [OH-] = sqrt(Kw). Thus [H+] = sqrt(2.7 x 10^-14) = 1.64 x 10^-7 M. pH = -log(1.64 x 10^-7) = 6.78.
pH = 6.78.
(a) OH- equivalents from Ca(OH)2 = 2(0.010 x 0.2) = 0.0040 mol; H+ from HCl = 0.025 x 0.1 = 0.0025 mol. Excess OH- = 0.0015 mol in 0.035 L, so [OH-] = 0.0429 M and pH = 12.63. (b) H2SO4 provides 0.0002 mol H+ and Ca(OH)2 provides 0.0002 mol OH-, so the mixture is neutral and pH = 7.00. (c) H2SO4 provides 0.0020 mol H+ and KOH provides 0.0010 mol OH-. Excess H+ = 0.0010 mol in 0.020 L, so [H+] = 0.050 M and pH = 1.30.
(a) pH = 12.63; (b) pH = 7.00; (c) pH = 1.30.
Using Table 6.9: Ksp(Ag2CrO4)=1.1 x 10^-12, so Ksp=(2S)^2S=4S^3 and S=6.50 x 10^-5 M. Ksp(BaCrO4)=1.2 x 10^-10, so S=sqrt(Ksp)=1.10 x 10^-5 M and both ions have this concentration. Ksp(Fe(OH)3)=1.0 x 10^-38, so Ksp=S(3S)^3=27S^4 and S=1.39 x 10^-10 M. Ksp(PbCl2)=1.6 x 10^-5, so Ksp=S(2S)^2=4S^3 and S=1.59 x 10^-2 M. Ksp(Hg2I2)=4.5 x 10^-29, so Ksp=S(2S)^2=4S^3 and S=2.24 x 10^-10 M.
Ag2CrO4: S = 6.50 x 10^-5 M, [Ag+] = 1.30 x 10^-4 M, [CrO4^2-] = 6.50 x 10^-5 M. BaCrO4: S = 1.10 x 10^-5 M. Fe(OH)3: S = 1.39 x 10^-10 M, [OH-] = 4.16 x 10^-10 M. PbCl2: S = 1.59 x 10^-2 M, [Cl-] = 3.17 x 10^-2 M. Hg2I2: S = 2.24 x 10^-10 M, [Hg2^2+] = 2.24 x 10^-10 M, [I-] = 4.48 x 10^-10 M.
For Ag2CrO4, Ksp = (2S)^2S = 4S^3, so S = (1.1 x 10^-12/4)^(1/3) = 6.50 x 10^-5 M. For AgBr, Ksp = S^2, so S = sqrt(5.0 x 10^-13) = 7.07 x 10^-7 M. Ratio = (6.50 x 10^-5)/(7.07 x 10^-7) = 92.
Molarity of saturated Ag2CrO4 solution : molarity of saturated AgBr solution = 92 : 1 approximately.
On mixing equal volumes, each concentration is halved: [Cu2+] = 0.001 M and [IO3-] = 0.001 M. For Cu(IO3)2, Qsp = [Cu2+][IO3-]^2 = (0.001)(0.001)^2 = 1.0 x 10^-9. Since Qsp < Ksp = 7.4 x 10^-8, the solution is unsaturated with respect to copper iodate and no precipitate forms.
No precipitation occurs.
For a salt of a weak acid in acidic buffer, S_buffer/S_water = sqrt(([H+] + Ka)/Ka). At pH 3.19, [H+] = 10^-3.19 = 6.46 x 10^-4 M. Therefore ratio = sqrt((6.46 x 10^-4 + 6.46 x 10^-5)/(6.46 x 10^-5)) = sqrt(11) = 3.32. Ksp cancels in the ratio.
Silver benzoate is about 3.32 times more soluble in the buffer.
Let the concentration of each original solution be C. After equal-volume mixing, [Fe2+] = C/2 and [S2-] = C/2. For no precipitation, Qsp must not exceed Ksp: (C/2)(C/2) = C^2/4 = 6.3 x 10^-18 at the limit. Therefore C = 2sqrt(6.3 x 10^-18) = 5.02 x 10^-9 M.
Maximum concentration of each original equimolar solution = 5.02 x 10^-9 M.
For CaSO4 ⇌ Ca2+ + SO4^2-, Ksp = S^2. Thus S = sqrt(9.1 x 10^-6) = 3.02 x 10^-3 mol L^-1. Molar mass of CaSO4 ≈ 136.1 g mol^-1, so solubility in g L^-1 = (3.02 x 10^-3)(136.1) = 0.411 g L^-1. Volume needed for 1.0 g = 1.0/0.411 = 2.43 L.
Minimum volume = 2.43 L.
After mixing, [S2-] = (1.0 x 10^-19)(10/15) = 6.67 x 10^-20 M and [M2+] = (0.04)(5/15) = 1.33 x 10^-2 M. Thus Qsp = [M2+][S2-] = 8.89 x 10^-22. Compare with Ksp values from Table 6.9: FeS = 6.3 x 10^-18 and MnS = 2.5 x 10^-13, so Qsp < Ksp and no precipitate forms. For ZnS = 1.6 x 10^-24 and CdS = 8.0 x 10^-27, Qsp > Ksp, so ZnS and CdS precipitate.
Precipitation will take place with ZnCl2 and CdCl2 only.