Carrasco Yana Grover Josue Carlos - 1419120032, PDF 17

17 ASPECTOS ADICIONALES
EQUILIBRIO DE ACUOSOS
Visualización de conceptos
17.1 Analizar. Dados diagramas que muestran mezclas de equilibrio de HX y X -

con diferentes composiciones, decidir cuál tiene el pH más alto. HX es un ácido
débil y X- es su base conjugada. Plan. Evalúe el contenido de los cuadros. Utilice
los principios de equilibrio ácido-base para relacionar [H*] con la composición del
cuadro. Resolver.
Utilice el siguiente equilibrio de ionización ácida para describir las mezclas:
HX(aq) (aq) + X- (aq). Cada caja tiene 4 moléculas HX, pero diferentes
cantidades de X -
Iones. Cuanto mayor sea la cantidad de X - (base conjugada), para la misma
cantidad de HX (ácido débil), menor será la cantidad de Fl* y mayor será el pH. La
caja central, con la mayoría de las X-, tiene al menos 11* y pH más alto.
17.2 a) Según la Figura 16.7, el metilanaranja es amarillo por encima del pH 4.5 y
rojo (en realidad rosa) por debajo del pH 3.5. El vaso de precipitados de la
izquierda tiene un pH mayor que 4,5, y el de la derecha tiene un pH inferior a 3,5.
(Por cálculo, pH del vaso de precipitados izquierdo s 4,7, pH del vaso derecho a
2,9.) El vaso de precipitados derecho, con pH más bajo y mayor [1111, es ácido
acético puro. El vaso de precipitados izquierdo con tiene cantidades iguales del
ácido débil y su base conjugada, ácido acético y ion de acetato. La adición del
acetato de iones comunes (en forma de acetato de sodio) desplaza el equilibrio de
ionización ácida hacia la izquierda, disminuye [111] y aumenta el pH.
(b) Cuando se añaden pequeñas cantidades de NaOH, el vaso de precipitados
izquierdo es mantener su pH. Para las soluciones del mismo ácido débil, el pH
depende de la relación entre la base conjugada y el ácido conjugado. Pequeñas
adiciones de base (o ácido) tienen el menor efecto cuando esta relación es dosis a
uno. El vaso de precipitados izquierdo es un tampón porque contiene un par de
base conjugado conjugado débil y resiste el rápido cambio de pH tras la adición de
pequeñas cantidades de base fuerte o ácido.
17.3 [HX] > [Xi. Búferes preparados a partir de ácidos débiles (FIX) y sus bases
conjugadas (X-, generalmente en forma de sal) tienen valores de pH en un rango
de aproximadamente 2 unidades de pH, centrados alrededor de pKa para el ácido
débil. Si la concentración del ácido débil es mayor que la concentración de la base
conjugada, pH < pKa. Si la concentración de la base conjugada es mayor que la
concentración del ácido débil, pH > pKa. Esto es generalmente cierto para los
tampones que contienen un par de ácido conjugado débil (CA) y base conjugada
(CB).
[CA] > [CB], pH del buffer < pIC de CA
[CA] < [CB], pH del buffer > pKa de CA
17 Aspectos Adicionales de las Soluciones a los Ejercicios

Equilibria acuoso
17.4 Analizar/Planificar. Cuando se añade ácido fuerte a un tampón, reacciona con

la base conjugada (CB) para producir ácido conjugado (CA). [CA] aumenta y [CB]
disminuye. Lo contrario ocurre cuando se agrega una base fuerte a un búfer, [CB]
aumenta y [CA] disminuye.
Haga coincidir estas situaciones con los dibujos. Resolver.
El búfer comienza con concentraciones iguales de HX y X -.
(a) Después de la adición de ácido fuerte, [HX] aumentará y [X -] disminuirá. Dibujo
(3) se ajusta a esta descripción.
(b) La adición de una base fuerte hace que [HX] disminuya y [X-] aumente. Dibujo
(1)
coincide con la descripción.
(c) El dibujo (2) muestra que [HX] y [X -] son más pequeños que los
concentraciones mostradas a la izquierda. Esta situación no puede lograrse
añadiendo
ácido fuerte o base fuerte al tampón original.
17.5 Analizar/Planificar. Considere la reacción HA + OH - -4 A + H2O. ¿Cuáles son
los principales
especies presentes en solución en las etapas enumeradas de la valoración? ¿Qué
diagrama
representa a estas especies? Resolver.
(a) Antes de la adición de NaOH, la solución es principalmente HA. La única A - es
producida por
el equilibrio de ionización de HA y es demasiado pequeño para aparecer en el
diagrama. éste
situación se muestra en el diagrama que contiene solamente HA.
(b) Después de la adición de NaOH, pero antes del punto de equivalencia,
algunos, pero no todos, HA ha
se ha convertido a A-. La solución contiene una mezcla de HA y A-; esto se
muestra en el diagrama (i).
(c) En el punto de equivalencia, toda ha convertida en A, sin exceso de HA o
Oh, presente. Esto se muestra en el diagrama (iv).
(d) Después del punto de equivalencia, la misma cantidad de A - está presente que
en la equivalencia
punto, además de un poco de exceso OH-. Este es el diagrama (ii).
17.6 Analizar/Planificar. En cada caso, la primera sustancia está en el buret, y la
segunda está en el
flask. If acid is in the flask, the initial pH is low; with base in the flask, the pH starts
high. Strong acids have lower pH than weak acids; strong bases have higher pH
than weak bases. Polyprotic acids and bases have more than one "jump" in pH.
(a) Strong base in flask, pH starts high, ends low as acid is added. Only diagram
(ii)
fits this description.
(b) andWeak acid in flask, pH starts low, but not extremely low. Diagrams (i),
(iv) all start at low pH and get higher. Diagram (i) has very low initial pH, and likely
has strong add in the flask. Diagram (iv) has two pH jumps, so it has a polyprotic
acid in the flask. Diagram (iii) best fits the profile of adding a strong base to a weak
add.
(c) Strong acid in the flask, pH starts very low, diagram (i).
(d) Polyprotic acid, more than one pH jump, diagram (iv).
17 Additional Aspects of Solutions to Exercises
Aqueous Equilibria
17.7 Analyze. Given two titration curves where 0.10 M NaOH is the titrant, decide
which
represents the more concentrated acid, and which the stronger acid.
Plan. For equal volumes of acid, concentration is related to volume of titrant (0.10
M NaOH) at the equivalence points. To determine Ka, pH = pKa half -way to the
equivalence point.
Solve.
(a) Both acids have one ionizable hydrogen, because there is one "jump" in each
titration curve. For equal volumes of acid, and the same titrant, the more
concentrated acid requires a greater volume of titrant to reach equivalence. The
equivalence point of the blue curve is at 25 mL NaOH, the red curve at 35 mL
NaOH. The red acid is more concentrated.
(b) According to the Henderson-Hasselbach equation, pH = pKa + log [conj. base] •

[conj. acid]
At half-way to the equivalence point, [conj. acid] = [conj. base] and pH = plca of the
conjugate acid. For the blue curve, half -way is 12.5 mL NaOH. The pH at this
volume is approximately 7.0. For the red curve, half -way is 17.5 mL NaOH. The pH
at this volume is approximately 4.2. A plc, of 7 corresponds to K. of
1 x l0-7, while pIC of 4.2 corresponds to K. of 6 x 10 -5. The red acid has the larger
K. value.
Note that the stronger acid, the one with the larger K. value, has a larger change in
pH (jump) at the equivalence point. Also note that initial add pH was not a
definitive measure of acid strength, because the acids have different starting
concentrations. Both
K. values and concentration contribute to solution pH.
17.8 Analyze/Plan. The beaker of saturated Cd(OH)2(aq) contains undissolved
Cd(OH)2(s),
Cd2+(aq), and OH-(aq). Decide how amounts of each of these three components
change when HC1(aq) is added. Solve.
Cuando se agrega HC1(aq), reacciona con OH-(aq) para formar H20(1) y Cl-(aq).
(Ambos han sido omitidos de la figura.) Cuando OH-(aq) se elimina de la solución,
más Cd(OH)2(s) se disuelve para reemplazarlo; [Cd2+(aq)] aumenta, [OH - (aq)]
disminuye y la cantidad de Cd(OH)2(s) no disuelto(s) disminuye. En la solución
resultante, [Cd2+(aq)] es mayor que [OH-(aq)] y hay menos sólido no disuelto en la
parte inferior del vaso de precipitados. El vaso de precipitados A representa con
precisión la solución después de restablecer el equilibrio.
17.9 Analizar/Planificar. Los aniones u cationes comunes disminuyen la solubilidad
de las sales. Iones que
participar en equilibrios de iones complejos o de base ácida aumentan la
solubilidad. Resolver.
(a) CO23- de BaCO3 reacciona con H+ de HNO3, causando solubilidad de BaCO3
a
aumentar con el aumento de la concentración de HNO3. Este comporta miento
coincide con el diagrama correcto.
(b) Co23 adicional- de Na2CO3 disminuye la solubilidad de BaCO3. Solubilidad de
BaCO3 disminuye a medida que aumenta [Na2CO3]. Este comportamiento coincide
con el diagrama izquierdo.
17 Aspectos Adicionales de las Soluciones a los Ejercicios
Equilibria acuoso
c) NaNO3 no tiene iones comunes, ni entra en iones ácido -base o complejos

equilibrios con Ba2+ o C032-; no afecta a la solubilidad de BaCO3. Este
comportamiento se muestra en el diagrama ce ntral.
17.10 Analizar/Planificar. Calcule la molaridad de la solución suponiendo que se
disuelva toda la(OH)2(s) Ca(OH)2(s).
Utilice esta concentración junto con la expresión Ksp para Ca(OH)2 para
questions.
0.370 g Ca (OH)2 1 mol Ca(OH)2
(a) [Ca(OH)2 X = 0.00998745 = 0.00999 M
0.500 L sole 74.093 g Ca(OH)2
[Call = 0.00999 M; [OW] = 2(0.00998745) = 0.0199749 = 0.0200 M;
Ksp = [Ca2l-][OH-12. Calculate the reaction quotient using the calculated

molarities. If it is equal to or greater than Ksp, the resultin g solution is saturated.
Q = (0.0098745)(0.0199749)2 = 3.99 x 10-6.
Q < Ksp (6.5 x 10-6) and the solution is not saturated.
(b) Consider the beakers individually.
(i) The 50 mL of 1.0 M HG is more than enough to neutralize 50 mL of
0.0200 M (aq). No precipitate forms.
NaG does not react with Ca(OH)2 and the two compounds contain no common
ions. No precipitate forms.
CaC12 does contain a common ion. Calculate Q for the resulting solution to see if
Ca(OH)2 precipitates. [OH-] in the new solution is 0.00999 M, because it is diluted
by a factor of 2. [Ca21] = (1.0 + 0.00999)/2 = 0.5050 M.
Q = (0.5050)(0.00999)2 = 5.04 x 10-5.
Q > Ksp (6.5 x 10-6) and Ca(OH)2 precipitates.
(iv) A common ion with a different concentration; = (0.10 + 0.00999)/2 =
0.0550 = 0.055 M. Q = (0.0550)(0.0999)2 = 5.49 x 10-6. Q p Ksp (6.5 x 10-6); the
solution is very nearly saturated, but no precipitate forms.
17.11 A metal hydroxide that is soluble at very low and very high pH's, that is, in
strong acid
or strong base, is called amphoteric.
17.12 According to Figure 17.23, the two precipitating agents are 6 M HO (first)
and H2S in
0,2 M HG (segundo).
Cation A - Ag+ (precipita como AgG)
Cation B - Cu+ (precipita como CuS, ácido insoluble) Cation C - Ni2+ (permanece
en solución ácida)
Efecto de iones comunes (sección 17.1)
17.13 a) El grado de ionización de un electrolito débil disminuye cuando un fuerte
electrolito que contiene un ion en común con el electrolito débil se añade a él.
(b) NaNO2
17.14 (a) Para una base débil genérica B, Kb á [HB+I
pH-1
Soluciones a los ejercicios

. Si una fuente externa de H13+
[B]
como HB+ Cl - se añade a una solución de B(aq), [HB+] aumenta, disminuyendo
[OH -] y aumentando [B], suprimiendo efectivamente la ionización (hidrólisis) de B.
(b) NH4C1
17.15 Analizar/Planificar. Siga la lógica en Ejercicio de ejemplo 17.1.
(a) C2H5COOH(aq) (aq) C2H5C00-(aq)
i 0.085 M 0.060 M
C -x +x +x
e (0,085 - x) M +xM (0,060 + x) M
Ka a 1,3 x 10-5 á [H+] [C2H5C00-] _ (x) (0,060 + x) [C2H5COOH] (0.085 - x)
Supongamos que x es pequeño en comparación con 0.060 y 0.085.

0.060 x1,3 x 10-5 x x 1,8 x 10-5 á [H+], pH a 4,730.085
Comprobar. Dado que el grado de ionización de un ácido o base débil es suprimido
por el
presencia de una sal conjugada, la regla del 5% generalmente se mantiene en
soluciones tampón.
Kb á 6,4 x 10-5 á [01-1 -] [(CH3)3NH+ ]
[(CE13)3N]
(CH3)3NH+(aq) + (aq)
0,10 M+x +x(0.10 + x) M +xM(x) (0,10 + x) 0,10 x(0.075 - x) 0.075
x á 4,8 x 10-5 á [OH-], p0H a 4,32, pH a 14,00 - 4,32 a 9,68

Comprobar. En un tampón, si [conj. ácido] > [base conj.], pH < pKa del ácido conj.
If [conj. acid] < [conj. base], pH > pKa of the conj. acid. In this buffer, pKa of
(CH3)3NH+ is 9.81. [(CH3)3N11+] > [(CH3)3N] and pH = 9.68, less than 9.81.
(c) mol = M x L; mol CH3COOH = 0.15 M x 0.0500 L = 7.5 x 10 -3 mol

mol CH3C00- = 0.20M x 0.0500 L = 0.010 mol
CH3COOH(aq) H+ (aq) + CH3C00-(aq)
7.5 x 10-3 mol 0 0.010 mol
c -x +x +x
e (7.5 x 10-3 -x) mol +x mol (0.010 + x) mol
[CH3COOH(aq) ] = (7.5 x 10-3 - x) mol/0.1000 L; [CH3C00-(aq)] = (0.010 + x)
mo1/0.1000 L
= [W ] [CH3C00-] (x) (0.010 + x)/0.1000 L x(0.010)
Ka =1.8 x 10-5
[CH3COOH] (0.0075 - x)/0.1000 L 0.0075
x= 1.35 x 10-3M = 1.4 x 10-3M H+; pH = 4.87
Check. pKa for CH3COOH = 4.74. [CH3C00-] > [CH3COOH], pH of buffer = 4.87,
17.16 Analyze/Plan. Follow the logic in Sample Exercise 17.1. Solve.
(a) HCOOH is a weak acid, and HCOONa contains the common ion HC00 -, the
conjugate base of HCOOH. Solve the common-ion equilibrium problem.
HCOOH(aq)i 0.100 Mc -xe (0.100 - x) M
[H+] [HC00-]H+ (aq) HC 00- (aq)0.250 M+x +x+x M (0.250 + x) M(x) (0.250 + x) N 0.250 x
Ka =1.8 x 10-4
[HCOOH] (0.100 - x) 0.100
x = 7.20 x 10-3 = 7.2 x 10-5 M = [H+], pH = 4.14
Check. Since the extent of ionization of a weak acid or base is suppressed by the
presence of a conjugate salt, the 5% rule usually holds true in buffer solutions.
(b) C5H5N is a weak base, and C5H5NHC1 contains the common ion C5H5NH+,
which is the conjugate acid of C5H5N. Solve the common ion equilibrium
problem.
C5H5N(aq) + H20(1) C5H5NH+ (aq) + OH-( (aq)

i 0.510 M 0.450 M
c -x +x +x
e (0.510 - x) M (0.450 + x) M +x M
(0.450 + x) (x) 0.450 x
Kb = 1.7 x 10-9 = [C5H5NH+] [OH- ]
[C5H5N] - (0.510 - x) 0.510
x = 1.927 x 10-9 = 1.9 x 10-9M = [OH-], p0H = 8.715, pH = 14.00 - 8.715 = 5.29
Check. In a buffer, if [conj. acid] > [conj. base], pH < pKa of the conj. acid.
If [conj. acid] < [conj. base], pH > pKa of the conj. acid. In this buffer, pKa of
C5H5NH+ is 5.23. [C5H5NH+] < [C5H5N] and pH = 5.29, greater than 5.23.
(c) mol = M x L; mol HF = 0.050 M x 0.055 L = 2.75 x 10 -3 = 2.8 x 10-3 mol;

mol F- = 0.10 M x 0.125 L = 0.0125 = 0.013 mol
HF(aq) H+(aq) F-(aq)i 2.75 x 10-3 mol 0 0.0125 mol-x +x +xe (2.75 x 10-3 - x) mol
+x (0.0125 + x) mol
[HF] = (2.75 x 10-3 + x)/0.180 L; [F-] = (0.0125 + x)/0.180 L
Note that the volumes will cancel when substituted into the Ka expression.
K = 6S x 10-4 = [11+][r] - x(0.0125 + x)/0.180
[HF] (2.75 x 10-3 - x)/0.180
x = 1.50 x 10-4= 1.5 x 10-4MH+; pH= 3.83
x(0.0125)0.00275
Check. pKa for HF = 3.17. [HP] < [F-], pH of buffer = 3.83, greater than 3.17.
17.17 Analyze/Plan. We are asked to calculate % ionization of (a) a weak acid and
(b) a weak
acid in a solution containing a common ion, its conjugate base. Calculate %
ionization as in Sample Exercise 16.13. In part (b), the concentration of the
common ion is 0.085 M,
not x, as in part (a). buCOOH(aq)equil (a) 0.0075- x equil (b) 0.0075- x M
Solve.
H+ (aq) + buC00- (aq) K.x M x Mx M 0.085 + x M2x2 X= [H+] [buC00 -] _ 1.5 x 10-3
[buCOOH]
(a) Ka =1.5 x 10-3 = 0.0075 - x 0.0075 ;x =[Fr] = 33.4 x 10-4 M H+ .354 x 10-4 =
3.4 x 10-4 MH+
(b)
% io a on = x 100 = 4.5% ionizationniz ti 0.0075 M buCOOH (x) (0.085+x) 0.085 x_6
Ka =1.5 x 10-5 x = 1 3 x 10 M H+
0.0075-x 0.0075
1.3 x 10-6 MH+
% ionization = x 100 = 0.018% ionization

0.0075 M buCOOH
Check. Percent ionization is much smaller when the "common ion" is present
17.18
CH3CH(OH)COOH H+ (aq)
equil (a) 0.125 - x M x M
equil (b) 0.125 - x M x M
Ka = [H+] [CH3CH(OH)C00-] =1.4 x 10-4 [CH3CH(OH)COOH]2+ CH3CH(OH)C00-

x M
0.0075 + x M
(a) Ka =1.4 x 10-4 = X0.125 -x4.2 xX2; x =[H+]= 4.18 x0.12510-3 M H+

10-3 M == 44..22 x 10-3 MH+
% ionization = x 100 = 3.4% ionization
0.125 M CH3CH(OH)COOH
(x) (0.0075 + x)
(b) Ka =1.4 x 10-4 °°75' x=2.3 x 10-3 M

0.125 - x 0.125
2.3 x 10-3 M H+
°l°ionization = x 100 = 1.9% ionization
0.125 M CH3CH(OH)COOH
Buffered Solutions (section 17.2)
17.19 CH3COOH and CH3COONa are a weak conjugate acid/conjugate base pair
which acts
as a buffer because unionized CH3COOH reacts with added base, while CH3C00 -
combines with added acid, leaving [111 relatively unchanged. Although Ha and
NaC1 are a conjugate acid/conjugate base pair, is a negligible base. That is, it has
no tendency to combine with added acid to form molecular HC1. Any added acid
simply increases [H+] in an HC1/NaC1 mixture. In general, the conjugate bases of
strong acids are negligible and mixtures of strong acids and their conjugate salts
do not act as buffers.
17.20 NaOH is a strong base and will react with CH3COOH to form CH3COONa. As
long as
CH3COOH is present in excess, the resulting solution will contain both the
conjugate acid CH3COOH(aq) and the conjugate base CH3C00 - (aq), the
requirements for a buffer.
mmol = M x mL; mmol CH3COOH = 1.00 M x 100 mL = 10.0 mmol mmol NaOH =
0.100 M x 50 mL = 5.0 mmol
CH3COOH (aq) + NaOH(aq) CH3COONa (aq) + H20(1)
initial 10.0 mmol 5.0 mmol
after rx 5.0 mmol 0 5.0 mmol
Mixing these two solutions has created a buffer b y partial neutralization of the
weak
acid CH3COOH.
17.21 Analyze/Plan. Follow the logic in Sample Exercise 17.3. Assume that %
ionization is
small in these buffers (Solutions 17.17 and 17.18). Solve.
K [W1 [CH3CH(OH)C00- [Ka [CH3CH(OH)COOH]
(b)
a [CH3CH(OH)C001-1] [CH3CF(OH)C00-]1.4 x 10-4 (0.12) [1-1+] = ; 1H+] = 1.53 x

10-4 = 1.5 x 10-4M; pH = 3.82
( 11)
mol = M x L; total volume = 85 mL + 95 mL = 180 mL
p+1. Ka[CH3CH(OH)COOH] 1.4 x 10-4 (0.13 M x 0.085 L)/0.180 L
[CH3CH(OH)C00-] - (0.15 M x 0.095 L)/0.180 L
1.4 x 10-4 (0.13 x 0.085)
[}11 =; [H+] = 1.086 x 10-4 = 1.1 x 10-4M; pH = 3.96 (0.15 x0.095)

17.22 Assume that % ionization is small in these buffers (Solutions 17.17 and
17.18).
(a) The conjugate acid in this buffer is HCO3 -, so use Ka2 for H2CO3, 5.6 x 10-11
K [HCO3-] 5.6 x 10-11 (0.105)
K = [Hl[C032-]a [H - 2_ =
[H+] = 4.70 x 10-11 = 4.7 x 10-11M; pH = 10.33

mol = M x L; total volume = 140 mL = 0.140 L
[H+] = Ka (0.20 M x 0.065 L)/0.140 L -5.6 x 10-11 (0.20 x 0.065)
(0.15 M x 0.075 L)/0.140 L (0.15 x 0.075)
[H+] = 6.47 x 10-11 = 6.5 x 10-11M; pH = 10.19
17.23 (a) Analyze/Plan. Follow the logic in Sample Exercises 17.1 and 17.3. As in
Sample
Exercise 17.1, start by calculating concentrations of the components. Solve.
CH3COOH(aq) H+(aq)+ CH3C00-(aq); Ka = 1.8 x 10-5 [H+] [CH3C00-]

[CH3COOH]
[CH3COOH] = 0.150 M
1 mol CH3COONa
[CH3C00-] = 20.0 g CH3COONa x - 0.488 M
0.500 L soln 82.04 g CH3COONa
[H+] Ka [CH3COOH] 1.8 x 10-5 (0.150 - x) 1.8 x 10-5 (0.150)
[CH3C00-] (0.488 + x) (0.488)
[H+] = 5.533 x 10-6 = 5.5 x 10-6 M, pH = 5.26

(b) Plan. On the left side of the equation, write all ions present in solution after HO
or NaOH is added to the buffer. Using acid-base properties and relative
strengths, decide which ions will combine to form new products. Solve.
Na+(aq) + H3C 00 (aq) + H + (aq) + Cl- (aq) CH3COOH(aq) + Na + (aq) + (aq)
(c) CH3COOH(aq) + Na+(aq) + OHlaq) --+CH3COOlaq) + H20(1) + Na+ (aq)
17.24 NH4+ /NH3 is a basic buffer. Either the hydrolysis of NH3 or the di ssociation
of NI-I4+
can be used to determine the pH of the buffer. Using the dissociation of NH4+
leads
directly to [H+] and facilitates use of the Henderson -Hasselbach relationship.
(a) NH4+ (aq) H+ (aq) + NH3(aq)
K = Kw - 1.0 x 10-14 - 5.56 x 10-1° = 5.6 x 10-1°a Kb 1.8 x 10-5

[NH3] = 1.00 M NH3
[NH41 10.0 g NH4C1 x 1 mol NH4C1
0.74766 = 0.748 M NH4+
0.250 L 53.50 g NH4C1
Ka = [H+] [NH3];H [ +]. Ka [NH4+]

[NH4+] [NH3]
Solutions to Exercises
5.56 x 10-1° (0.74766 - x) 5.56 x 10-10 (0.74766)(1.00 + x) (1.00)
[WE] = 4.1537 x 10-1° = 4.15 x 10-1° M, pH = 9.382

17.25
(b) NH3(aq) + H+(aq) + NO3-(aq) -> NH4+ (aq) + NO3- (aq)
(c) NH4+ (aq) + Cl- (aq) K+ (aq) + OH-(aq) -> NH3(aq) + H20(1) C1-(aq) + K+ (aq)
Analyze/Plan. Follow the logic in Sample Exercise 16.12 and 17.4. Solve.
(a) Ka =6.8 x 10-4 =1.00 - x 1.00

• x = [H+] = 0.02608 = 0.026 M; pH = 1.58
There is 2.6% ionization, so the approximation is valid.

(b) In this problem, [F-] is the unknown.
pH = 3.00, [H+] = 10-3.°° = 1.0 x 10-3; [HF] = 1.00 - 0.0010 = 0.999 M
1.0 x 10 [F-];
Ka = 6.8 x 10-4 =
0.999
0.6793 mol NaF x 41.990 g NaF
1 L 1 mol NaF
17.26 (a) C6H5COOH(aq) H+ (aq)j 0.6793 = 0.68 M x 1.25 L = 35.654 36 g NaF
+ C6H5C00-(aq)
Ka = 6.3x 10-5 = [H+] [C6H5C00]; [C 6 H5 COOH] = 0.0200 M;

[C6H5COOLts]
[H+] á [C6H5C00-] á xy2

Ka á 6.3 x 10-5 - • x á [H+] á 1.123x 10-3 x 1.1 x 10-3M; pH 2,95
0.02000
Tenga en cuenta que C6H5COOH está activado al 5,6%. La resolución de los
resultados cuadráticos para [H+]
(1.0914 x 10-3 ) 1.1 x 10-3 M H+, pH a 2.96; esto no es una diferencia
significativa.
(b) [H+]- Ka [C6H5C-H] ; [H] á 10 'xi á 1,0 x 10-4 M
[C6H5C00-]
[C6H5COOH] a 0,0200 M; calcular [C6H5C00-]. Porque el ion común
C6H5C00- reduce % de ionización, suponemos que la aproximación del 5% es
válida.
K [C6H5COOH] 6.3 x 10-5 (0.0200)
[C6H5C00-] a +[H0.0126 mol C6H5COONa L
• 0,01260 a 0,013 M
1.0 x 10-4 x1.50 L x 144.11 g C6H5COONa
1 mol C6H5COONa2,724 x 2,7 g C6H5COONa
17.27 Analizar/Planificar. Siga la lógica de los ejercicios de ejemplo 17.3 y 17.5.

Resolver.
(a) Ka - [H+] [CH3C00-] ; - Ka [CH3COOH]

[CH3COOH] [CH3C00-]
▪
17 Aspectos adicionales de
Equilibria acuoso
1.8 x 10-5 (0.10)
Soluciones a los ejercicios
[H+] tf 1.385 x 10_5 á .4 x1 10-5 M; pH 4,86

(0.13)
(b) CH3COOH(aq) + KOH(aq) - CH3C00-(aq) + H20(1) + Klaq)
0.10 mol 0.02 mol 0.13 mol
-0.02 mol -0.02 mol +0.02 mol
0.08 mol 0 mol 0.15 mol
[H1 a 1,8 x 10-5 (0,08 mo1/1,00 L) a 9,60 x 10-6 x 1 x 10-5 M; pH a 5,02 a 5,0
(0.15 mo1/1.00 L)
(c) CH3C00-(aq) + HN 03 (aq) - CH3COOH(aq) + NO3-(aq)

0.13 mol 0.02 mol 0.10 mol
-0.02 mol -0.02 mol +0.02 mol
0.11 mol 0 mol 0.12 mol
1,8 x 10-5 (0,12 mol/1,00 L)

17.28 (a)
[H+] á 1,96 x 10-5 x 2,0 x 10-5 M; pH 4,71

(0.11 mo1/1.00 L)
Ka [H+][C2H5C001; [H+] á Ka [C2H5COOH][C2H5COOH][C2H5C00]

Since this expression contains a ratio of concentrations, we can ignore total
volume and work directly with moles.
[H+] =
1.3 x 10-5 (0.15 - x)

(0.10 + x)
1.3 x 10-5 (0.15) .

0.10
1.950 x 10-5 = 2.0 x 10-5 M, pH = 4.71
(b)
+ OH- (aq) -÷ C2H5COOH(aq)
0.15 mol 0.01 mol
-0.01 mol -0.01 mol
0.14 mol 0 mol
1.3 x 10-5 (0.14) =
C2H5C00-(aq) + H20(1)
0.10 mol
+0.01 mol
0.11 mol
[H+]
(0.11)
(c) C2H5c00-(aq) +
0.10 mol
-0.01 mol
0.09 mol
1.3 x 10 (0.16) _
1.6545 x 10-5 = 1.7 x 10-5 M; pH = 4.78
IH(aq) -+ C2H5COOH(aq) + I-(aq)

0.01 mol 0.15 mol
-0.01 mol +0.01 mol
0 mol 0.16 mol
[W] ft
2.3111 x le = 2 x 10-5 M; pH= 4.6
(0.09)
512
Aqueous Equilibria
17.29 Analyze/Plan. Calculate the [conj. base]/ [conj. acid] ratio in the
H2CO3}HCO3- blood
buffer. Write the acid dissociation equilibrium and Ka expression. Find Ka for
H2CO3
in Appendix D. Calculate [F1*] fr om the pH and solve for the ratio. Solve.
q) q) [H+] [HCO3-] [HCO3
H2CO3(aq) (a +HCO3- (a
Ka =
[ H 2 CO 3] [H 2 CO 3]
[H+]
[HCO3- ] _ 4.3 x 10-7

(a) at pH = 7.4, [H+] =10-7'4 = 4.0 x 104 M; 11
[H2CO3] 4.0 x 10-8
8 [HC031 _5
(b)
at pH = 7.1, [H+] = 7.9 x 10- M; .4

[H2CO3]
6.5 gNaH2PO4 x 1 mol NaH2PO4

17.30 = 0.153 = 0.15 M
0.355 L soln 120 g NaH2PO4
8.0 gNa2HPO4 x 1 mol Na2HPO4

= 0.159 = 0.16 M
0.355 L soln 142 g Na2HPO4
Use Equation [17.9] to find the pH of the buffer. Ka for H2PO4- is Ka2 for H3PO4,
6.2 x 10-8
0.159
pH = -log (6.2 x10-8) + log - - 7.2076 +0.0167 = 7.22
0.153
17.31 Analyze. Given six solutions, decide which two should be used to prepare a
pH 3.50
buffer. Calculate the volumes of the two 0.10 M solutions nee ded to make
approximately 1 L of buffer.
Plan. A buffer must contain a conjugate acid/conjugate base (CA/CB) pair. By
examining the chemical formulas, decide which pairs of solutions could be used to
make a buffer. If there is more than one possible pair, calculate pKa for the acids.
A buffer is most effective when its pH is within 1 pH unit of pKa for the conjugate
acid component. Select the pair with pKa nearest to 3.50. Use Equation [17.9] to
calculate the [CB]/ [CA] ratio and the volumes of 0.10 M solut ions needed to
prepare 1 L of buffer.
Solve.
There are three CA/CB pairs:
HCOOH/HCOONa, pKa = 3.74
CH3COOH/CH3COONa, pKa = 4.74
H3PO4/NaH2PO4, pKa = 2.12

The most appropriate solutions are HCOOH/HCOONa, because pKa for HCOOH is
nearest to 3.50.
[HCOONa]
pH = pKa + log 5; 3.50 = 3.7447 + log
[HCOOH]
[HCOONa] [HCOONa]
log = -0.2447; - 0.5692 = 0.57
[HCOOH] [HCOOH]
Since we are making a total of 1 L of buffer,
let y = vol HCOONa and (1 - y) = vol HCOOH.
513
17 Additional Aspects of
Aqueous Equilibria
(0.10 M x y)/1L
0.5692 = [HCOONa] _ 0.5692[0.10(1- y)] = 0.10 y;

[HCOOH] [0.10 M x (1- y)] /1 L
0.05692 = 0.15692 y; y = 0.3627 = 0.36 L
360 mL of 0.10 M HCOONa, 640 mL of 0.10 M HCOOH.
Check. The pH of the buffer is less than pKa for the conjugate acid, indicating that
the amount of CA in the buffer is greater than the amount of CB. This agrees with
our result.
17.32 The solutes listed contain three possible conjugate acid/conjugate base
(CA/CB) pairs.
These are:
HCOOH/HCOONa, pKa = 3.74
CH3COOH/CH3COONa, pKa = 4.74 HCN/NaCN, pKa = 9.31
For maximum buffer capacity, pKa should be within 1 pH unit of the buffer. The
acetic acid/acetate pair are most appropriate for a buffer with pH 5.00.
pH = pKa +log [C13] • 5.0000 = 4 745 +log [CH3COONa]
[CA] * [CH3COOH]
log [CH3COONa] = 0.2553; [CH3COONa] =1.800 = 1.8

[CH3COOH] [CH3COOH]
Since we are making a total of 1 L of buffer,

let y = vol CH3COONa and (1- y) = vol CH3COOH.
(0.10 M x y)/1.0 L 0.10 y
1.800 - [CH3COONa]
[CH3COOH] [0.10 M x (1- y)]/1.0 L 0.10 -0.10 y
1.800(0.10 - 0.10 y) = 0.10 y; 0.1800 = 0.2800 y; y = 0.6429 = 0.64 L 640 mL of
0.10 M CH3COONa, 360 mL CH3COOH
Check. pH (buffer) > pKa (CA) and the calculated amount of CB in the buffer is
greater than the amount of CA.
Acid-Base Titrations (section 17.3)
17.33 (a) Curve B. The initial pH is lower and the equivalence point region is
steeper.
(b) pH at the approximate equivalence point of curve A = 8.0
pH at the approximate equivalence point of curve B = 7.0
(c) Volume of base required to reach the equivalence point depends only on moles
of
acid present; it is independent of acid strength. Since acid B requires 40 mL and
acid A requires only 30 mL, more moles of acid B are being titrated. For equ al
volumes of A and B, the concentration of acid B is greater.
17.34 (a) The quantity of base required to reach the equivalence point is the same
in the
two titrations, assuming both sample solutions contain equal moles of acid.
514
Aqueous Equilibria
(b) The pH is higher initially in the titration of a weak acid.

(c) The pH is higher at the equivalence point in the titration of a weak acid.
(d) The pH in excess base is essentially the same for the two cases.
(e) In titrating a weak acid, one needs an indicator that changes at a higher pH
than
for the strong acid titration. The choice is more critical because the change in pH
close to the equivalence point is smaller for the weak acid titration.
17.35 (a) False. The same volume of NaOH(aq) is required to reach the
equivalence point
of both titrations, because moles of acid to be titrated are the same in both flasks.
(b) True. CH3COONa, the salt formed in the titration of CH3COOH, produces a
basic solution, while NaNO3, formed in the titration of HNO3 produces a neutral
solution.
(c) True. Even though the pH values at the equivalence points of the two titrations
are different, phenolphthalein changes color over a wide range of pH values and is
appropriate for both titrations.
17.36 (a) False. The pH at the beginning of the titration of the weaker acid,
CH3COOH,
will be higher.
(b) True. Past the equivalence point, the titration curves are very similar (but not
identical.
(c) False. According to Figures 17.13 and 17.14, methyl red is suitable for the
titration of the strong acid HNO3, but not for the titration of the weak acid
CH3COOH.
17.37 Analyze. Given reactants, predict whether pH at the equivalence point of a
titration is
less than, equal to or greater than 7.
Plan. At the equivalence point of a titration, only product is present in solution;
there is
no excess of either reactant. Determine the product of each reaction and whether a
solution of it is acidic, basic or neutral. Solve.
(a) NaHCO3 (aq) + NaOH(aq) —› Na2CO3(aq) + H20(1)
At the equivalence point, the major species in solution are Na* and C032 -. Na* is
negligible and C032- is the CB of HCO3-. The solution is basic, above pH 7.
(b) NH3 (aq) + HC1(aq) —› NH4C1(aq)
At the equivalence point, the major species are NH4* and Q. Cl- is negligible, NH4*
is the CA of NH3. The solution is acidic, below pH 7.
(c) KOH(aq) + HBr(aq) —› KBr(aq) + H20(1)
At the equivalence point, the major species are K+ and Br -; both are negligible.
The solution is at pH 7.
17.38 (a) HCOOH(aq) + NaOH(aq) —› HCOONa(aq) + H20(1)
At the equivalence point, the major species are Na* and HC00 -. Na* is negligible
and HCOO- is the CB of HCOOH. The solution is basic, above pH 7.
515
Aqueous Equilibria
(b) Ca(OH) 2(aq) + 2HC104(aq) -+ Ca(C104)2(aq) + 21120(1)

At the equivalence point, the major species are Ca2+ and C104 -; both are
negligible. The solution is at pH 7.
(c) C5H5N(aq) + HNO3(aq) -+ C5H5NH+ NO3- (aq)
At the equivalence point, the major species are C5H5NH+ and NO3 -. NO3- is
negligible and C5H5NH+ is the CA of C5H5N. The solution is acidic, below pH 7.
17.39 The second color change, from yellow to blue near pH = 8.5, is more suitable
for the
titration of a weak acid with a strong base. The salt present at the equivalence
point of this type of titration produces a slightly basic solution. The second color
change of Thymol blue is in the correct pH range to show (indicate) the
equivalence point.
17.40 (a) At the equivalence point, moles HX added = moles B initially present =
0.10 M x 0.0300 L = 0.0030 moles FIX added.
(b) BH+ (aq)
(c) Both Ka for BH+ and concentration BH+ determine pH at the equivalence point.
(d) Because the pH at the equivalence point will be less th an 7, methyl red would
be
more appropriate.
17.41 Analyze/Plan. We are asked to calculate the volume of 0.0850 M NaOH
required to
titrate various add solutions to their equivalence point. At the equivalence point,
moles base added equals moles acid initially present. Solve the stoichiometry
problem, recalling that mol = M x L. In part (c) calculate molarity of HO from g/L
and proceed as outlined above. Solve.
0.0900 mol HNO3 1 mol NaOH 1000 mL soln
(a)
(b)
40.0 mL HNO3 x x x
1000 mL soln 1 mol HNO3 0.0850 mol NaOH
= 42.353 = 42.4 mL NaOH soln
1 mol NaOH x 1000 mL soln

35.0 mL CH3COOH x 0.0850 M CH3COOH x
1000 mL soln 1 mol CH3COOH 0.0850 mol NaOH
= 35.0 mL NaOH soln

1.85 g HC1 x 1 mol HCl
(c) = 0.05074 = 0.0507 M HC1

1 L soln 36.46 g HC1
0.05074 mol HC1 1 mol NaOH 1000 mL soln
50.0 mL HC1
17.42 (a)
x x
1000 mL 1 mol HC1 x 0.0850 mol NaOH
= 29.847 = 29.8 mL NaOH soln
1 mol HO x 1000 mL soln
45.0 mL NaOH x 0.0950 mol NaOH x
1000 mL soln 1 mol NaOH 0.105 mol HQ
= 40.7 mL HO soln
516
Aqueous Equilibria
(b) 22.5 mL NH3 x 0.118 mol NH3

1000 mL soln
1 mol HC1 1000 mL soln

x x
1 mol NH3 0.105 mol HC1
= 25.3 mL HCl soln
(c) 125.0 mL x 1.35 g NaOH

1000 mL
1 mol NaOH 1 mol HC1 1000 mL soln

x
40.00 g NaOH x 1 mol NaOH x 0.105 mol HC1
= 40.2 mL HCl soln
17.43 Analyze/Plan. Follow the logic in Sample Exercise 17.6 for the titration of a
strong acid
with a strong base. Solve.
moles H+ = MHBr X LHBr = 0.200 M x 0.0200 L = 4.00 x 10'3 mol
moles OW = M NaOH X LNaOH = 0.200 M X LNaOH
Total Moles Molarity

MLHBr mi-NaOH Volume Moles H+ OH' Excess Ion pH
(a) 20.0 15.0 35.0 4.00 x 10-3 3.00 x 10-3 0.0286(H+) 1.544
(b) 20.0 19.9 39.9 4.00 x 10-3 3.98 x 10-3 5 x 10-4(1-1+) 3.3
(c) 20.0 20.0 40.0 4.00 x 10-3 4.00 x 10-3 1 x 10-7(H') 7.0
(d) 20.0 20.1 40.1 4.00 x 10-3 4.02 x 10-3 5 x 104(OH-) 10.7
(e) 20.0 35.0 55.0 4.00 x 10-3 7.00 x 10-3 0.0545(0W) 12.737
molarity of excess ion = moles ion / total vol in L
4.00 x 10-3 mol H+ -3.00 x 10-3 mol
(a)
0.0350 L
4.00 x 10-'3 mol Fr -3.98 x 10-3 mol OH-

(b)
0.0339 L
(c) equivalence point, mol H' = mol OH-
- 0.0286 M H+
=5.01 x 10-4 =5 x 10-4 M H+
NaBr does not hydrolyze, so [W] = [OH-] =1 x 10-7M

(d) 4.02
x 10-3 mol OH- -4.00 x 10

0.0401 L
-3
mol
= 4.99 x 110-4= 5 x 10-4 M OH-
7.00 x 10-3 mol OW -4.00 x 10-3 mol Fr+

(e)
0.0550 L
-0.054545=0.0545MOH-
17.44 moles OH- = A wl./ X LKOH = 0.150 M x 0.0200 L = 3.00 x 10-3 mol
moles H+= ---mHao, X LHC104 = 0.125 M x LHao4

517
Aqueous Equilibria
Total
Molarity Excess
mLKOH IIILHao4
(a) 20.0 20.0
(b) 20.0 23.0

(c) 20.0 24.0
(d) 20.0 25.0
(e) 20.0 30.0
Volume Moles 01'- Moles H+

40.0 3.00 x 10-3 2.50 x 10-3
43.0 3.00 x 10-3 2.88 x 10-3
44.0 3.00 x 10-3 3.00 x 10-3
45.0 3.00 x 10-3 3.13 x 10-3
50.0 3.00 x 10-3 3.75 x 10-3
Ion pH
0.013(OH-) 12.10
2.9 x 10-3(OH-) 11.46
1.0 x 10-7(OH-) 7.00
2.8 x 10-3(H+) 2.56
0.015(H+) 1.82
molarity of excess ion = moles ion

total vol in L
3.00 x 10-3 mol OH- -2.50 x 10-3 mo1H+

0.0400E
- 0.0125 = 0.013 M OH-
3.00 x 10-3 mo101-1- - 2.875 x 10-3 mol H+

0.0430 L
equivalence point, mol H+ = mol OH-
- 2.91 x 10-3 = 2.9 x 10-3 M OH-
KCIO4 does not hydrolyze, so [H+] = [OH-] =1 x 10-7M
3.125 x 10-3 mol W -3.00 x 10-3 mol OH-

0.0450 L
3.75 x 10-3 mol W -3.00 x 10-3 mol OH-
-2.78 x 10-3 = 2.8 x 10-3 M H+
=0.0150 = 0.015 M 1-1+

0.0500 L
17.45 Analyze/Plan. Follow the logic in Sample Exercise 17.7 for the titration of a
weak add
with a strong base. Solve.
(a) At 0 mL, only weak add, CH3COOH, is present in solution. Using the acid
ionization equilibrium
CH3COOH(aq) H+ (aq) + CH3C00-(aq)
Initial 0.150 M 0 0
equil 0.150 - x M xM xM
Ka - [H+][CH3C°°-] =1.8 x 10-5 (Appendix D)

[CH3COOH]
x2
1.8 x 10-5 =
(0.150- x)
y2
; x2 = 2.7 x 104; x = [H+] = 0.001643
0.150
=1.6 x 10-3 M; pH = 2.78
(b)-(f) Calculate the moles of each component after the acid -base reaction takes
place.
Moles CH3COOH originally present = M x L = 0.150 M x 0.0350 L = 5.25 x 10 -3
mol.
Moles NaOH added = M x L = 0.150 M x y mL.
518
Aqueous Equilibria
NaOH(aq) + CH3COOH (aq) -> CH3COONa(aq) + H20(1)

(0.150 M x 0.0175 L) =
(b) before rx 2.625 x 10-3 mol 5.25 x 10-3 mol
after rx 0 2.625 x 10-3 mol 2.63 x 10-3 mol
(0.150 M x 0.0345 L) =
(c) before rx 5.175 x10-3 mol 5.25 x 10-3 mol
after rx 0 0.075 x 10-3 mol 5.18 x 10-3 mol
(0.150 M x 0.0350 L) =
(d) before rx 5.25 x 10-3 mol 5.25 x10-3 mol
after rx 0 0 5.25 x 10-3 mol
(0.150 M x 0.0355 L) =
(e) before rx 5.325 x 10-3 mol 5.25 x 10-3 mol
after rx 0.075 x 10-3 mol 0 5.25 x 10-3 mol
(0.150 M x 0.0500 L) =
(f) before rx 7.50 x 10-3 mol 5.25 x 10-3 mol
Calculate the molarity of each species (M= mol/L) and solve the appropriate
equilibrium problem in each part.
(b) VT = 35.0 mL CH3COOH + 17.5 mL NaOH = 52.5 mL = 0.0525 L
2.625 x 10-3 mol
[CH3COOH] =
[CH3C00-] =
0.0525
2.625 x 10-3 mol
0.0525
- 0.0500 M
= 0.0500 M
CH3COOH(aq)
equil 0.0500 - x M
K -[H+][CH3C00-]
F1*(aq) + CH3C00-(aq)
x M 0.0500 + x M
a ; [H+ = Ka [CH3COOH:]]
[CH3COOH] [CH3C00-]
10-5 (0.0500-x) -
[Ha] -1.8 x 1.8 x 10-5 M F1+; pH = 4.74
(0.0500 + x)
(c) [CH3COOH] = 7.5 x 10-5 mol - 0.001079 = 1.1 x 10-3 M

0.0695 L
519
Aqueous Equilibria
5.175 x 10-3 mol
[CH3C00-] =
0.0695 L
= 0.07446 = 0.074 M
[H+] = 1.8 x 10-5 (1.079 x
10-3 - x)
2.6 x 10-7 M H+; pH = 6.58
(0.07446 + x)
(d) At the equivalence point, only CH3COO - is present

5.25 x 10-3 mol
[CH3C00-] - = 0.0750 M
0.0700 L
The pertinent equilibrium is the base hydrolysis of CH3COO -.
CH3C00-(aq) + H20(1) initial 0.0750 M

equil 0.0750 - x M
K 1.0 x
____
..-- CH3COOH(aq) + OH-(aq)
0 0
x x
10-14
Kb - =
Ka for CH3COOH 1.8 x 10-5
X2
= 5.56 x 10-10 = 5.6 x 10-10 = [CH3COOH] [OW]

[CH3C00-]
5.56 x 10-10 = ; x2 = 5.56 x 10-10 (0.0750); x = 6.458 x 10-6

0.0750 - x
=6.5 x 10-6 M OH-
p0H = -log(6.458 x 10-6) = 5.19; pH = 14.00 - pOH = 8.81
(e) After the equivalence point, the excess strong base determines the pOH and
pH.
The [OH-] from the hydrolysis of CH3C00- is small and can be ignored.
[OH-1= 0.075 x 10-3 mol = 1.064 x 10-3 = 1.1 x 10-3 M; pOH = 2.97
0.0705 L
pH = 14.00-2.97 = 11.03
2.25 x 10-3 mol

(f)
17.46 (a)
[01-1-] = = 0.0265 M OH-; pOH = 1.577; pH = 14.00 -1.577 =12.423

0.0850 L
[NH4+ ] [OH-] Weak base problem: Kb = 1.8 x 10-5
[NH3]
At equilibrium, [OH-] = x, [NH3] = (0.030 - x); [NH4+] = x
1.8 x 10-5 =
x2 X2
(0.050 - x) 0.050
; X = [OH- ] = 9.487 x 10-4 = 9.5 x 10-4 M
pH = 14.00 - 3.02 = 10.98

(b-f) Calculate mol NH3 and mol NH4÷ after the acid -base reaction takes place.
0.050 M NH3 x 0.0300 L = 1.5 x 10-3 mol NH3 present initially.
520
Aqueous Equilibria
NH3(aq) HC1(aq) NH4* (aq) + Cl- (aq)

(0.025 M x 0.0200 L) =
(b) before rx 1.5 x 10-3 mol 0.50 x 10-3 mol 0 mol
after rx 1.0 x 10-3 mol 0 mol 5.0 x 10-4 mol
(0.025 M x 0.0590 L) =
(c) before rx 1.5 x 10-3 mol 1.475 x 10-3 mol 0 mol
after rx 2.5 x 10-5 mol 0 mol 1.475 x 10-3 mol
(0.025 M x 0.0600 L) =
(d) before rx 1.5 x 10-3 mol 1.5 x 10-3 mol 0 mol
after rx 0 mol 0 mol 1.5 x 10-3 mol
(0.025 M x 0.0610 L) =
(e) before rx 1.5 x 10 -3 mol 1.525 x 10-3 mol 0 mol
after rx 0 mol 2.5 x 10-5 mol 1.5 x 10-3 mol
(0.025 M x 0.0650 L) =
(f) before rx 1.5 x 10-3 mol 1.625 x 10-3 mol 0 mol
after rx 0 mol 1.25 x 10-4 mol 1.5 x 10-3 mol
(b) Using the acid dissociation equilibrium for NH4*

directly), NH4+ (aq) H+ (aq) + NI -13(aq)
[H+ ] [NH3] 1.0 x 10-14 5 56
K
(so that we calculate [111
x 10-10 = 5.6 x 10-1°

= =
[NH4*]
w
Kb for NH3 = 1.8 x 10-5 =
[NH3]= 1.0 x 10-3 mol = 0.020 M; [NH4+ ] = 5.0 x 10-4 mol

0.0500 L 0.0500 L
5.56 x 10-10 (0.010) .
= 0.010 M
[H+ ]= 536 x 10-1° [NH4+] 2.78 x 10-1°; pH = 9.56

[NH3] (0.020)
(We will assume [H+] is small compared to [NH3] and [NH4].)+
(c) [NH3] = 2.5 x 10-5 mol = 2.8 x 10-4

0.0890 L
10-10 (0.017) =
+
M; [NFI4
1.475 x 10-3 mol
0.0890 L
- 0.017 M
[H+]= 5.56 x 3.38 x 104 = 3.4 x 10-5 M; pH = 7.47

(2.8 x 10-4)
(d) At the equivalence point, [H+] = [NH3] = x
10-3 M
[NH4+] = 1.5 x
0.0900 L
= 0.01667 = 0.017 M
521
Aqueous Equilibria
X2
5.56 x 10-10= ; x = [H+ ] = 3.043 x 10-6 = 3.0 x 10-6 M; pH = 5.52

0.01667
(e) Past the equivalence point, [H+] from the excess HG determines the pH.
[H+ ]= 2.5 x 10-5 mol - 2.747 x 10 = 2.7 x 10 M; pH = 3.56

0.0910 L
(f) Past the equivalence point, [H+] from the excess HO determines the pH.
10-4 mol
[H+]= 1.25 x -1.316 x 10-3 =1.3 x 10-3 M; pH = 2.88
0.0950 L
17.47 Analyze/Plan. Calculate the pH at the equivalence point for the titration of
several bases
with 0.200 M HBr. The volume of 0.200 M HBr required in all cases equals the
volume of base and the final volume = 2Vbase. The concentration of the salt
produced at the
equivalence point is 0.200 M X Vbase = 0.100 M.
2Vbase
In each case, identify the salt present at the equivalence point, determine its acid-
base
properties (Section 16.9), and solve the pH problem. Solve.
(a) NaOH is a strong base; the salt present at the equivalence point, NaBr, does
not
affect the pH of the solution. 0.100 M NaBr, pH = 7.00
(b) HONH2 is a weak base, so the salt presen t at the equivalence point is
HONH3+Br- . This is the salt of a strong acid and a weak base, so it produces an
acidic solution.
0.100 M HONH3+ Br; HONH3+(aq) H+ (aq) + HONH2
[equil] 0.100 - x
[Fr] [HONH2] - 1.0 x 10-14
Ka = - 9.09 x 10-7 = 9.1 x 10-7
[HONH3+] Kb 1.1 x 10-8
Assume x is small with respect to [salt].
Ka = x2 / 0.100; x = [H+] = 3.02 x 10-4 = 3.0 x 10-4M, pH = 3.52
(c) C6H5NH2 is a weak base and C6H5N1 -13+ Br is an acidic salt.

0.100 M C6H5NH3+ Br -. Proceeding as in (b):
K = [H+] [C6H5NH2] - - 2.33 x 10-5 = 2.3 x 10-5

[C6H5NH3+] Kb
[H12 = 0.100(2.33 x 10-5); [H+] = 1.52 x 10-3= 1.5 x 10-3M, pH = 2.82
17.48 The volume of NaOH solution required in all cases is

vb Vacid x Madd (0.100) Vacid
1.25 Vacid
Mbase (0.080)
522
Aqueous Equilibria
The total volume at the equivalence point is Vbase Vacid = 2.25 Vacid•
The concentration of the salt at the equivalence point is Macid
Vacid 00.100
= 0.0444 M
2.25 Vacid 2.25
(a) 0.0444 M NaBr, pH = 7.00

(b) 0.0444 M NaC1O2; C102- (aq) + H20(1) HC102(aq) + OH-(aq)
. 1.0 x 10-14
=[HC102][0H-] = 9.09 x 10-13 =9.1 x 1043
[C1021 Ka 1.1 x 10-2
[HC102] = [OH-]; [C102-] rz 0.0444 M
[OH-]2 z 0.0444(9.09 x 10-13); [OH-] = 2.01 x 10-7= 2.0 x 10-7M, pOH = 6.70;
pH = 7.30
Note that HC1O2 is a relatively strong acid (large Ka value), so the pH at the
equivalence point is not much greater than 7.0. Since [OH -] from the hydrolysis of
C102- is very small, the autoionization equilibrium should be considered for a more
accurate value of the equivalence point pH.
Let [F1+] = x, [OH-] = (2.0 x 10-7M + x); 1.0 x 10-14 = (x)(2.0 x 10-7M + x) Solving
the quadratic equation gives a pH of 7.38.
(c) C6H5C00-(aq) + H20(1)
[C6H5C00-1 [OW]
Kb =
[C6H5COOF1] Ka
C6H5COOH(aq) + OH-(aq)
. 1.0 x 10-14
, =1.59 x 10-1° =1.6 x 10-1°
6.3 x
PH-12 0.0444(1.59 x 10-8); [OH-] = 2.655 x 10-6 = 2.7 x 10-6, pH = 8.42

Solubility Equilibria and Factors Affecting Solubility
(sections 17.4 and 17.5)
17.49 (a) The concentration of undissolved solid does not appear in the solubility
product
expression because it is constant as long as there is solid present. Concentration
is a ratio of moles solid to volume of the solid; solids occupy a specific volume not
dependent on the solution volume. As the amount (moles) of solid changes, the
volume changes proportionally, so that the ratio of moles solid to volume solid is
constant.
Analyze/Plan. Follow the example in Sample Exercise 17.9. Solve.
K p
= [Ag+][I -]; Ks p
= Fr21 [50421; Kap = [Fe21 [OH -]2; K p

= [Hg221 [Br - ]2
Solubility is the amount (grams, moles) of solute that will dissolve in a certain
volume of solution. Solubility-product constant is an equilibrium constant, the
product of the molar concentrations of all the dissolved ions in solution.
Ks p = [Mn21 [C032-]; Ks p = [Hg 2 1 [OH 1 2; Kap = [C11213[P043 -]2
523
Aqueous Equilibria
(a) CaF2(s) Ca 2 + (aq) + 2F- (aq); Ks p = [Ca21[F-] 2
The molar solubffity is the moles of CaF2 that dissolve per liter of solution. Each
mole of CaF2 produces 1 mol Ca2+(aq) and 2 mol F - (aq).
[Ca2+] = 1.24 x 10-3 M; [F-] = 2 x 1.24 x 10-3 M = 2.48 x 10-3 M
Ksp = (1.24 x 10-3) (2.48 x 10-3)2 = 7.63 x 10-9
]
SrF2(s) Sr 2 + (aq) (aq); Ks p = [S
(b) + 2F r 21 [F- 2
Transform the gram solubffity to molar solubility.
1.1 x 10-2 g SrF2 x 1 mol SrF2 . _4

8.76 x 10-4 = 8.8 x 10 mol SrF2 /L
0.100 L 125.6 g SrF2
[Sr2+] = 8.76 x 10-4 M; [F-] = 2(8.76 x 10-4 M)
Ks p = (8.76 x 10-4) (2(8.76 x 10-4))2 = 2.7 x 10-9
] ]
(c) Ba(I03) 2 (S) Ba 2 + (aq) + 2103-(aq); Ks p = [Ba [I03 2
Since 1 mole of dissolved Ba(I03) 2 produces 1 mole of Ba2+, the molar solubffity
of
Ba(I03)2 = [Ba2 3 Let x = [Ba2+]; [103-] = 2x
Ksp = 6.0 x 10-10 = (x)(2x)2; 4x3 = 6.0 x 10-10; x3 = 1.5 x 10-10; x= 5.3 x 10-4 M
The molar solubility of Ba(I03) 2 is 5.3 x 10 -4 mol/L.
17.52 (a) PbBr2(s) Pb 2 + (aq) + 2Br (aq)
Ksp = [Pb2+][Br-] 2; [Pb21 =1.0 X 10-2 M, [Br-] = 2.0 x 10-2 M
Ksp = (1.0 x 10-2 M)(2.0 x 10-2 M)2 = 4.0 x 10-6
(b) AgI03(s) Ag+ (aq) + 103- (aq); Ks p = [Ag+][103-]
0.0490 g Ag103 1 mol AgI03

[Agl= [I03-]- =1.733 x 10 =1.73 x 10 M
1.00L soln 282.8 g Ag103
Ks p = (1.733 x 10-4 M) (1.733 x 10-4 M) = 3.00 x 10-8
(c) Ca(OH) 2 (S) 7,= Ca 2+ (aq) + 20H- (aq); Ks p = [Ca 21[OH -] 2
[Ca2+] = x, [OH-] = 2x; Ks p =

6.5 x 10-6 = (x)(2x) 2
6.5 x 10-6 = 4x3; x = [Ca2+] = 0.01176 = 0.012 M; [OH-] = 0.02351 = 0.024 M
pH = 14 - p0H = 14 - 1.629 = 12.37
17.53 Analyze/Plan. Given gram solubffity of a compound, calculate Ks p. Write the

dissociation equilibrium and Ksp expression. Change gram solubility to molarity of
the individual ions, taking the stoichiometry of the compound into account.
Calculate Ksp.
Solve.
524
Aqueous Equilibria
CaC2O4 (s) Ca2+(aq) + C2042-(aq); Ksp = Ka21[C20421

0.0061 g CaC2O4 1 mol CaC2O4
[Ca 2+
= [C20421= X - 4.76 x
1.00 L soln 128.1g CaC2O4
Ksp = (4.76 x 10-5 M)(4.76 x 10-5M) = 2.3 x 10-9
17.54 PbI2(s) Pb2+(aq) + 2I-(aq); Ksp = [Pb2+][1-]2
[pb2+ .54 g PbI2 x 1 mol PbI2
10-5 = 4.8 x
10-5 M
]. 0 =1.17 x 10-3 =1.2 x 10-3 M

1.00 L soln 461.0 g PbI2
[I-] = 2[Pb2+]; Ks p = [Pb21(2[Pb21)2 = 4[Pb2+] 3 = 4(1.17 x 10 -3)3 = 6.4 x 10-9
17.55 Analyze/Plan. Follow the logic in Sample Exercises 17.11 and 17.12. Solve.
(a) AgBr(s) Ag+ (aq) + Br-(aq); Ksp = [Ag+][Br-] = 5.0 x 10-13
molar solubility = x = [Ag+] = [Br]; Ksp = x2
x = (5.0 x 10-13)1/2; x = 7.1 x 10-7 mol AgBr/L
(b) Molar solubility = x = [Br]; [Ag+] = 0.030 M + x
Ksp = (0.030 + x)(x) 0.030(x)
5.0 x 10-13= 0.030(x); x= 1.7 x 10-11 mol AgBr/L
(c) Molar solubility = x = [Ag+]
There are two sources of Br-: NaBr(0.10 M) and AgBr(x M)
Ksp = (x)(0.10 + x); Assuming x is small compared to 0.10 M
5.0 x 10-13= 0.10 (x); x 5.0 x 10-12 mol AgBr/L
17.56 LaF3(s) La3+(aq) + 3F - (aq); K, p = [La3+ I [F

(a) molar solubility = x = [La3+]; [F-] = 3x
KSP= 2 x 10-19= (x)(3x)3; 2 x 10-19= 27 x4; x = (7.41 x 10-21)1/4, X = 9.28 x 10-6
= 9 x 10-6MLa'
9.28 x 10-6 mol L 195.9 g L
aF3 x aF3 _1.82 x 10-3 = 2 x 10-3 g LaF3 /L
1L 1 mol
(b) molar solubility = x = [LAI
There are two sources of F-: 10(0.010 M) and LaF3 (3x M)
Ksp = (x)(0.010 + 3x)3; assume x is small compared to 0.010 M.
2 x 10-19= (0.010)3 x; x = 2 x 10-19/1.0 x 10-6= 2 x 10-13M La"
2 x 10-13 mol LaF3 x 195.9 g F3 _
1L
La 3.92 x 10-11 = 4 x 10-11 g LaF3 IL

1 mol
525
Aqueous Equilibria
(c) molar solubility = x, [F-] = 3x, [La3+] = 0.050 M + x

K, p = (0.050 + x)(3x) 3; assume x is small compared to 0.050 M.
2 x 10-19= (0.050)(27 x3) = 1.35 x3; x = (1.48 x 10 -19)1/3 = 5.29 x 10-7= 5 x 10-
7M
529 x 10-7 mol LaF3 x

1 L
195.9 g LaF3
1.04 x 10-4 =1 x 10-4 g LaF3 /L
1 mol
17.57 Analyze/Plan. Given a saturated solution of CaF2 in contact with undissolved

CaF2(s),
consider the effect of adding CaC12(s). The two salts have the Cat, ion in common.
Solve. As CaC12 is added, [Ca21 increases, K, p is exceeded, and additional CaF2
precipitates until equilibrium is reestablished. At the new equilibrium position:
(a) The amount of CaF2(s) on the bottom of the beaker increases becau se the
added
Ca2* from CaC12 decreases the solubility of CaF2.
(b) The [Ca21 in solution increases because of the added CaC12.
(c) The [F-] in solution decreases because CaF2(s) precipitates upon addition of
CaC12. The product of [Ca21 and [F], the Ksp, is the same.
17.58 As KI is added, [11 increases, Ksp is exceeded, and additional PbI2

precipitates until
equilibrium is reestablished. At the new equilibrium position:
(a) The amount of PbI2 (s) on the bottom of the beaker increases because the
added I-
from KI decreases the solubility of PbI2.
(b) The [Pb2] in solution decreases because PbI2 (s) precipitates upon addition of
KI.
(c) The [11 in solution increases because of the added KI. The product of [Pb2] and
[I-], the Ksp, is the same.
17.59 Analyze/Plan. We are asked to calculate the solubility of a slightly -soluble

hydroxide
salt at various pH values. This is a common ion problem; pH tells us not only but
also [OH-], which is an ion common to the salt. Use pH to calculate [OH 1, then
proceed as in Sample Exercise 17.12. Solve.
Mn(OH) 2 (S) Mn2*(aq) + 20H- (aq); K, p = 1.6 x 10-13
Since [OH-] is set by the pH of the solution, the solubility of Mn(OH) 2 is just
[Mn21.
(a) pH = 7.0, p0H = 14 - pH = 7.0, [OH
= 10-P°H = 1.0 x 10-7M

1.6 x 10-13
Ksp =1.6 x 10-13 =[Mn2+](1.0 x 10-7)2;
16 mol Mn(OH)2 x 88.95 g Mn(OH)2
[Mn2+]. 16 M
1.0 x 10-14 =
1423 = 1.4 x 103 g Mn(OH)2 /L

1 L 1 mol Mn(OH)2
Check. Note that the solubility of Mn(OH) 2 in pure water is 3.6 x 10 -5M, and the
pH of the resulting solution is 9.0. The relatively low pH of a solution buffered to
pH 7.0 actually increases the solubility of Mn(OH) 2.
526
Aqueous Equilibria
(b) pH = 9.5, p0H = 4.5, [OH-] = 3.16 x 10-5 = 3.2 x 10-5M

1.6 x 10-13
Ksp =1.6 x 10-13 = [Mn21(3.16 x 10-5)2; [Mn21 = 9 - 1.6 x 10-4 M
1.0 X 10-
1.6 x 10-4M Mn(OH)2 X 88.95 g/mol = 0.0142 = 0.014 g/L
(c) pH = 11.8, p0H = 2.2, [OH-] = 6.31 x 10-3= 6.3 x 10-3M

1.6 x 10-13
Ksp =1.6 x 10-13 = [Mn21(6.31 x 10-3)2; [Mn21 - = 4.0 x 10-9 M
3.98 x 10-5
4.02 x 10-9M Mn(OH)2 x 88.95 g/mol = 3375 x 10_7=3.6 x 10 -7 g/L
17.60 Ni(OH)2(s) Ni2+(aq) + 20H - (aq); Ks p
6.0 x 10-16
Since the [OH-] is set by the pH of the solution, the solubility of Ni(OH) 2 is just
[Ni21.
(a) pH = 8.0, p0H = 14 - pH = 6.0, [OH-] = 10-Pc" =1 x10-6M
6.0 x 10-16
Ksp - 6.0 x 10-16 = [Ni21(1.0 x 10-8)2; [Ni2+] =

1.0 x 10-12
(b) pH = 10.0, p0H = 4.0, [OH-] = 1.0 x 10-4 = 1 x 10-4 M
6.0 x 10-16
Ksp - 6.0 x 10-18 = [Ni2+][1.0 x 10-4]2; [Ni-, 1 =
1.0X10-'a
(c) pH = 12.0, p0H = 2.0, [OH'] = 1.0 x 10 -2 =1 x 10-2 M
2 2 .2+ 6.0 x 10-18
- 6.0 x 10-4 = 6 x 10-4 M
- 6.0 x 10-8 = 6 x 10-8 M
Ksp = 6.0 x 10-16 = [Ni2+1[1.0 x 10-1 ; [NI 1= - 6.0 x 10-12 = 6 x 10-12 M

1.0 X10-4
If the anion of the salt is the conjugate base of a weak acid, it will combine with 1 -
1+,
reducing the concentration of the free anion in solution, thereby causing more salt
to
dissolve. More soluble in acid: (a) ZnCO3, (b) ZnS, (d) AgCN, (e) Ba3(PO4)2
17.62 If the anion in the slightly soluble salt is the conjugate base of a strong acid,
there will
be no reaction.
(a) MnS(s) + 2H+ (aq) H2S(aq) + Mn2+(aq)
(b) PbF2(s) + 2H+ (aq) 2HF(aq) + Pb2+(aq)
(c) AuC13(s) + H+ (aq) -+ no reaction
(d) Hg2C204 (s) + 2H+ (aq) -> H2C204 (aq) + Hg22+(aq)
(e) CuBr(s) + (aq) -) no reaction
527
Aqueous Equilibria

The formation equilibrium is
[Ni NH 2+
Ni2+ (aq) + 6NH3(aq) Ni(NH3)62+(aq) Kf •••• x 109
[Ni2+] [NH3r
Assuming that nearly all the Ni2+ is in the form Ni(NH3)62+,

[Ni(NH3)62+] =1 x 10-3 M; [Ni2+] = x; [NH3] = 0.20 M
1 x 10 );
1.2 x 10, = ( x =1.30 x 104 =1 x 104 M =[Ni2+]
x(0.20)6
17.64 NiC2O4(s) Ni2+ (aq) + C2042-(aq); K.p = [Ni2+][C 2 0 1 = 4 x ln -10
When the salt has just dissolved, [C2042-] will be 0.020 M. Thus [Ni2+] must be
less than
4 x 10-16 / 0.020 = 2 x 104 M. To achieve this low [Ni2+] we must complex the
Ni2+ ion with NH3: Ni2+ (aq) + 6NH3 (aq) Ni(NH3)62+ (aq). Essentially all Ni(II) is
in the form of the complex, so [Ni(NH3)62+] = 0.020. Find Kf for Ni(NH3)62+ in
Table 17.1.
[Ni(NH3)+1 (0.020)
Kf = 2 =1.2 x 109; [NH3]6 = 8.33 x 10-4;
[Ni +J[NH3]6 (2 x 104) [NH3]6
[NH3]= 0.307 = 0.3 M
17.65 Analyze/Plan. Calculate the solubility of AgI in pure water according to the
method in
Sample Exercise 17.11. Obtain Keq for the complexaction reaction, making use of
pertinent K.p and Kf values from Appendix D and Table 17.1. Write the dissociation
equilibrium for Agl and the formation reaction for Ag(CN)2 -. Use algebra to
manipulate these equations and their associated equ ilibrium constants to obtain
the desired reaction and its equilibrium constant. Finally, use this Keq value to
calculate the solubility of AgI in 0.100 M NaCN solution. Solve.
(a) AgI(s) Ag+(aq) + I- (aq); K. p = [Ag+][1-] = 8.3 x 10-17
molar solubility = x = [Ag*] = [Ii; Ksp = x2
x = (8.3 x 10-17)1/2; X -= 9.1 x10-9 mol AgI/L
(b) AgI(s) Ag+(aq) + 1 (aq)
AgI(s) + 2CN- (aq) Ag(CN)2(aq) + I- (aq)
[Ag(CN 1
K= Ksp x Kf = [Agl[r] x = (8.3 x 10-17)(1 x 1021). 8 x 104
[Ag+1 [CN-]2
(c) K is much greater than one for the reaction of AgI(s) with CN-. This means that
the reaction goes to completion. For a AgI(s) in 0.100 M NaCN solution, CN - is the
limiting reactant. Two moles of CN- react with one mole of AgI, so the solublility of
AgI in 0.100 M NaCN is (0.100/2) = 0.0500 M.
528
Aqueous Equilibria
17.66 According to Table D-3, Ksp for Ag2S(s) is of the type
Ag2S(s) + H20(1) - 2Ag*(aq) + 1-1S-(aq) + OH-(aq)

HS- (aq) + H+ (aq) H2S(aq)
Ksp
1 /
Kal
2[Ag*(aq) + 2C1 (aq) r AgC12(ac)i
Ag2S(s) + H20(1) + H+ (aq) + 4C1- (an) 2AgC12(aq) + H2S(aq)
Add H* (aq) to each side to obtain the overall reacation

Ag2S(s) + 2H+ (aq) + 4C1- (aq) 2AgC12(aq) + H2S(aq)
Kf 2
K =
s x
P
K al
K f2 (6 x 10-51) (1.1 X 105)2

(9.5 x 10-8)
7.64 x 10-34 = 8 x 10-34
Precipitation and Separation of Ions (section 17.6)
17.67 Analyze/Plan. Follow the logic in Sample Exercise 17.15. Precipitation

conditions: will Q
(see Chapter 15) exceed Ksp for the compound? Solve.
(a) In base, Ca' can form Ca(OH) 2 (s).
Ca(OH) 2 (S) Ca 2 (aq) + 20H - (aq); Ksp = [Ca21[0H-] 2
Q = [Ca21[0H-] 2; [Ca2+] = 0.050 M; p0H = 14 - 8.0 = 6.0; [OH-] = 1.0 x 10-6M Q =
(0.050)(1.0 x 10-6)2 = 5.0 x 10-14; Ksp = 6.5 x 10-6 (Appendix D)
Q < Ksp, no Ca(OH)2 precipitates.
(b) Ag2SO4(s) 2Ag+ (aq) 93421 4 0

; Ksp = [Ag+1 2 [ 4 21
[AO = 0.050 M x 100 mL - 4.545 x
110 mL
0.050 M x 10 mL
[S042i =
110 mL
10-2 = 4.5 x 10-2 M
- 4.545 x 10-3 = 4.5 x 10-3 M
Q = (4.545 x 10-2)2 (4.545 x 10-3) = 9.4 x 10-6; Ksp = 1.5 x 10-8 Q < Ksp, no
Ag2SO4 precipitates.
17.68 (a) Co(OH) 2 (S)
Co2+(aq) + 20H-(aq); Ksp
=
[CO 2 1 [OH-] 2 = 1.3 x 10-18
pH = 8.5; p0H = 14 - 8.5 = 5.5; [OH-] = 10-8.8= 3.16 x 10-6= 3 x 10-6 M Q =

(0.020)(3.16 x 10-6)2 = 2 x 10-13; Q > Ksp, Co(OH)2 will precipitate
(b) Ag103(s) Aglaq) + 103- (aq); Ksp= [Ag+][I03-] = 3.1 x 10-8
[AO = 0.010 M Ag+ x 0.020 L = 6.667 x 10 -3 = 6.7 x 10-3 M

0.030 L
529
Aqueous Equilibria
0.015 M103- x 0.010 L [I03-] -

0.030 L
= 5.000 x 10-3= 5.0 x 10-3M
Q = (6.667 x 10-3)(5.00 x 10-3) = 3.3 x 10-3; Q > KSP, AgI03 will.precipitate
17.69 Analyze/Plan. We are asked to calculate pH necessary to precipitate

Mn(OH)2(s) if the
resulting Mn2+ concentration is 1 µg/L.
Mn(OH) 2 (S) Mn2+(aq) + 20H- (aq); Ksp = [Mn2+][0H-] 2 = 1.6 x 10-13
At equilibrium, [Mn2+][0H-] 2 = 1.6 x 10-13. Change concentration Mn2+(aq) to
mol/L
and solve for [OH-]. Solve.
1p.tg Mn2+ x 1 x 10-8 g x 1 mol Mn2+
=1.82 x 10-8 = 2 x 10-8 M Mn2+
1L 1µg 54.94 g Mn-+
1.6 x 10-13 = (1.82 x 10 -8) [OH-] 2; [OH-]2 = 8.79 x 10-6; [OH-] = 2.96 x 10-3 = 3
x 10-3M
p0H = 2.53; pH = 14 - 2.53 = 11.47 = 11.5
17.70 PbI2(s) Pb2+(aq) 2I-(aq); Ksp = [Pb2+][I-] 2 = 8.49 x 10-9
(This Ksp value is taken from CRC Handbook of Chemistry and Physics, 74th
Edition.)
_0 1/2
[pb2+ = 0.10 M x 0.2 mL

10.2 mL
=1.96 x10-3 = 2 x 10-3 M; [I-]=
8.49 x 10-
1.96 x 10-3M =
2.08 x10-3 =2 x 10-3M
2.08 x 10-3 mol I-

1 L
126.90 g I-
x x 0.0102 L = 2.69 x 10-3 g I- = 3 x 10-3 gl-
1 mol I-
17.71 Analyze/Plan. We are asked which ion will precipitate first from a solution
containing
Pb2+(aq) and Ag+ (aq) when I- (aq) is added. Follow the logic in Sample Exercise
17.16. Calculate [I-] needed to initiate precipitation of each ion. The cation that
requires lower
[I-] will precipitate first. Solve.
1017
Ag+ : KsP = [Ag+][I-1; 8.3 x 10-17 = (2.0 x
pb2+: Ksp = [pb2+ ][1- -
10-4)[I-1; [I-] = 8.3 x - 4.2 x 10-13 M I-

2.0 x 10-4
7 .9 x 10
]2; 7.9 x 1 - 0-9 = (1.5 x 10-3)[112;
AgI will precipitate first, at [I-] = 4.2 x 10-13M.
-93 1/2= 2.3 x 10-3 M I-

1.5 x 10-
17.72 (a) Precipitation will begin when Q = Ks

p a
BaSO4: Ks p = [Ba2+.][S042-] = 1.1 x 10-10

1.1 x 10-10 = (0.010)[S0421; [50421 = 1.1 x 10-8 M SrSO4: KSP = P.2+1[50421 =
3.2 x 10-7
3.2 x 10-7 = (0.010)[S0421; [S0421 = 3.2 x 10-5 M
530
Aqueous Equilibria
The [S0421 necessary to begin precipitation is the smaller of the two values,
1.1 x 10-8 M S042-.
(b) Ba2+ precipitates first, because it requires the smaller [50421
(c) Sr2+ will begin to precipitate when [S0421 in solution (not bound in Ba504)
reaches 3.2 x 10-5M.
17.73 Analyze/Plan. We are asked which ion will precipitate first when dilute Ag+
(aq) is
added to a solution containing 0.20 M Cr042 -, 0.10 M C032- and 0.10 M C1-. The
anions are present at different concentrations and their silver compound s have
different stoichiometry, so we cannot directly compare Ksp values. Follow the logic
in Sample Exercise 17.16. Calculate [Ag+] needed to initiate precipitation of each
ion. The anion that requires lowest [A gl will precipitate first, and so on. Solve .
Ag2CrO4: K, p = [Ag12[Cr0421 = 1.2 x 10 -12
1.2 x 10-12 = [Ag12(0.20); [Ag12 = 6.0 x 10 -12; [Agl = 2.4 x 10-6 M Ag2CO3: Ksp
=[Ag12[C032-] = 8.1 x 10-12
8.1 x 10-12 = [Ag12(0.10); [Ag12 = 8.1 x 10 -11; [AgE] = 9.0 x 10-6 M AgCl: Ks p =
[Agl[C1-] = 1.8 x 10-10
1.8 x 10-1° = [AO (0.10); [AO = 1.8 x 10-9
Aga requires the smallest [AO for precipitation and it will precipitate first. The other
two will precipitate almost simultaneously.
17.74 It is not appropriate to compare K, p values directly, because the

stoichiometries of the
the two precipitates are different
(a) Precipitation will begin when Q = Ks p.
CaSO4: Ksp = Ka21[50421 = 2.4 x 10-5
2.4 x 10-5 = (0.20)[50421; p0421 = 1.2 x 10 -4 M Ag2SO4: Ks p [Ag12[S042-] = 1.5
x 10-5
1.5 x 10-5 = (0.30)2[50421; [S0421 =1.7 x 10-4M
CaSO4 requires the smaller [S0421 for precipitation and it will precipitate first.
(b) The [S0421 necessary to begin precipitation is the smaller of the two values,
1.2 x 10-4M S042-.
1.0 M SO42- x X L
1.2 x 10_4 M =
(0.010 + x L)
; X = (0.010)1.2 x 10-4 =1.2 x 104 L.
We assume x is small compared to 0.010 L. The required volume is then

1.2 x 10-6 L or 0.0012 mL or 1.2 pL. If one drop is approximately 0.2 mL,
precipitation will begin as the first drop of 1.0 M Na2SO4 solution is add ed.
531
Aqueous Equilibria
Qualitative Analysis for Metallic Elements (section 17.7)
17.75 Analyze/Plan. Use Figure 17.23 and the description of the five qualitative
analysis
"groups" in Section 17.7 to analyze the given data. Solve.
The first two experiments eliminate Group 1 and 2 ions (Figure 17.23). The fact
that no insoluble phosphates form in the filtrate from the third experiment rules out
Group 4 ions. The ions which might be in th e sample are those of Group 3, that is,
A13+, Fe3+, Cr3+, Zn2+, Ni2+, Mn2+, or Co2+, and those of Group 5, NH4+, Na+
or K
17.76 Initial solubility in water rules out CdS and HgO. Formation of a precipitate
on addition
of HC1 indicates the presence of Pb(NO3)2 (formation of PbC12). Formation of a
precipitate on addition of H2S at pH 1 probably indicates Cd(NO3)2 (formation of
CdS). (This test can be misleading because enough Pb2+ can remain in solution
after filtering PbC12 to lead to visible precipitation of PbS.) Absence of a
precipitate on addition of H2S at pH 8 indicates that ZnSO4 is not present. The
yellow flame test indicates presence of Na+. In summary, Pb(NO3)2 and Na2SO4
are definitely present, Cd(NO3)2 is probably present, and CdS, HgO and ZnSO4
are definitely absent.
17.77 Analyze/Plan. We are asked to devise a procedure to separate various pairs
of ions in
aqueous solutions. In each case, refer to Figure 17.23 to find a set of conditions
where
the solubility of the two ions differs. Construct a procedure to generate these
conditions. Solve.
(a) Cd2+ is in Gp. 2, but Zn2+ is not. Make the solution acidic using 0.2 M HO;
saturate with H2S. CdS will precipitate, ZnS will not.
(b) Cr(OH)3 is amphoteric but Fe(OH)3 is not. Add excess base; Fe(OH)3(s)
precipitates, but Cr3* forms the soluble complex Cr(OH)4 -.
(c) Mg2+ is a member of Gp. 4, but K+ is not. Add (NH4)2HPO4 to a basic solution;
Mgt* precipitates as MgNH4PO4, K+ remains in solution.
(d) Ag+ is a member of Gp. 1, but Mn2+ is not. Add 6 M Ha p recipitate Ag+ as
AgCl(s).
17.78 (a) Make the solution slightly acidic and saturate with H2S; CdS will
precipitate,
Na+ remains in solution.
(b) Make the solution acidic, saturate with H2S; CuS will precipitate, Mg2+ remains
in solution.
(c) Add HG, PbC12 precipitates. (It is best to carry out the reaction in an ice -water
bath to reduce the solubility of PbC12.)
(d) Add dilute HG; AgC1 precipitates, Hg2+ remains in solution.
17.79 (a) Because phosphoric acid is a weak acid, the concentration of free P043 -
(aq) in an
aqueous phosphate solution is low except in strongly basic media. In less basic
media, the solubility product of the phosphates of interest is not exceeded.
(b) K91, for those cations in Group 3 is much larger. Thus, to exceed Ku , a higher
[S21 is required. This is achieved by making the solution more basic.
532
Aqueous Equilibria
(c) They should all redissolve in strongly acidic solution, e.g., in 12 M HCl (the
chlorides of all Group 3 metals are soluble).
17.80 The addition of (NH4)2HPO4 could result in precipitation of salts from metal
ions of
the other groups. The (NH4)2HPO4 will render the solution basic, so metal
hydroxides could form as well as insoluble phosphates. It is essential to separate
the metal ions of a group from other metal ions before carrying out the specific
tests for that group.
Additional Exercises
17.81 Analyze/Plan. Follow the approach for deriving the Henderson -Hasselbach
(H-H)
equation from the K. expression sho wn in Section 17.2. Begin with a general Kb
expression. Solve.
[BH+ ][0W]
B(aq) + I-I20(1) BHI-(aq) + OH- (aq); Kb =
[B]
pOH = -log[OH-]; rearrange Kb to solve for [OH-]. [OH-] = Kb [?1 ; take the -log of
both sides
[BH
-log[OH-] = -log Kb + (-log[B] - (-log[BH+] ) pOH = pKb + log[BH+] - log[B]
pOH = pKb + log [BH+ ]

[13]
17.82 Benzene sulfonic acid = BSOH, sodium benzene sulfonate = BSONa
Use Equation 17.9, pH = pKa + log [CB]/ [CA].
pH = 2.25 + log(0.125 M BSONa/0.150 M BSOH) pH = 2.25 + log(0.8333) = 2.25 +
(-0.0792) = 2.17
17.83 The equilibrium of interest is
HC5H303(aq) (aq) + C5H303-(aq); Ka = 6.76 x 10-4 = [11+
] [C5H3031
[HC5H303]
Begin by calculating [HC5H303] and [C5H303 -] for each case.
(a)
25.0 g HC5H303 x 1 mol HC5H303

0.250 L soln 112.1 g HC5H303
= 0.8921 = 0.892 M HC5H303
30.0 gNaC5H303 x 1 mol NaC5H3O3

0.250 L soln 134.1 g NaC5H3O3
= 0.8949 = 0.895 M C5H303-
+
[H ] =
Ka [HC5H303] =
1
[C51-1303
6.76 x 10-4 (0.8921-x) 6.76 x 10-4(0.8921)

(0.8949 + x) (0.8949)
[HI- ] = 6.74 x 10-4M, pH = 3.171
533
Aqueous Equilibria
(b) For dilution, M1 V1 = M2V2
[HC5H303] - 0.250 M x 30.0 mL
= 0.0600 M
125 mL
[C5H303] = 0.220 M x 20.0 mL = 0.0352 M

125 mL
[H+] N 6.76 x 10-4 (0.0600) -

0.0352
1.15 x 10-3 M, pH = 2.938
(yes, [H+] is < 5% of 0.0352 M)

(c) 0.0850 M x 0.500 L = 0.0425 mol HC5H303
1.65 M x 0.0500 L = 0.0825 mol NaOH
HC5H303(aq) + Na0H(aq) ,- NaC5H303(aq) F120(1)

initial 0.0425 mol 0.0825 mol
reaction -0.0425 mol -0.0425 mol +13.0425 mol
after 0 mol 0.0400 mol 0.0425 mol
The strong base NaOH dominates the pH; the contribution of C5H303 - is negligible.
This combination would be "after the equivalence point" of a titration. The tot al
volume is 0.550 L.
[OW] =
[H+][ ]
0.0400 mol
= 0.0727 M; pOH = 1.138, pH = 12.862
0.550 L
17.84 Ka - in ; at pH = 4.68, [Hirt] = [In

[Hirt]
]; [H+] = Ka; pH = pKa = 4.68
17.85 (a) HA(aq) + B(aq) HB+(aq)+ A-(aq) K = [HB+ ] [A

eq [HA] [B]
(b) Note that the solution is slightly basic because B is a stronger base than HA is
an
acid. (Or, equivalently, that A- is a stronger base than HB+ is an acid.) Thus, a
ilttle of the A- is used up in reaction: A- (aq) + H20(1) = HA(aq) + OH-(aq).
Since pH is not very far from neutral, it is reasonable to assume that the reaction
in part (a) has gone far to the right, and that [Al [H13+] and [HA] Pa [B]. Then
] [H+]
Ka - [A[H ] - 8.0 x 10-5; when pH = 9.2, [H+] = 6.31 x 10-10 = 6 x 10-10 M
[A-]
HA - 8.0 x 10-5/6.31 x 10-10 =1.268 x 105 =1 x 105
[ ]
From the assumptions above, [[HAA1 = [H[iBn+ ] , so Keq [[ -q122 -1.608 x 1010 =
2 x 10 10
(c) Kb for the reaction B(aq) + H20(1) BH+ (aq) +OH -(aq) can be calculated by
noting that the equilibrium constant for the reaction in part (a) can be written as K
= Ka (HA) x Kb (B) / Kw. (You should prove this to yourself.) Then,
534
Aqueous Equilibria
K x Kw (1.608 x
1010) (1.0 x 10-14) =
Kb (B) =
Ka (HA)
— 2.010= 2
8.0 x 10-5
Kb (B) is larger than Ka (HA), as it must be if the solution is basic.
17.86 (a) Ka =
[11+][HC00-]
[HCOOH]
[111 — Ka [HCOOH]
[HCOO-]
1.00 mol
Buffer A : [HCOOH] = [HCOO- ] — =1.00 M

1.00 L
1.8 x 10-4 (1.00 M)
[111 = = 1.8 x 10-4 M, pH = 3.74
(1.00 M)
Buffer B:[HCoom = [HCOO-] = 0.010 mol — 0.010 M

1.00 L
[H1
—1.8 x 10-4 (0.010 M)

(0.010 M)
1.8 x 10_4 M, pH = 3.74
The pH of a buffer is determined by the identity of the conjugate acid/ conjugate

base pair (that is, the relevant Ka value) and the ratio of concentrations of the
conjugate acid and conjugate base. The absolute concentrations of the
components is not relevant. The pH values of the two buffers are equal because
they both contain HCOOH and HCOONa and the [HCOOH] / [HCOO -] ratio is the
same in both solutions.
(b) Buffer capacity is determined by the absolute amount of conjugate acid and
conjugate base available to absorb strong acid (F1*) or strong base (OH -) that is
added to the buffer. Buffer A has the greater capacity because it contains the
greater absolute concentrations of HCOOH and HCOO -.
(c) Buffer A: HCOO- + HCl —> HCOOH + Cl-

1.00 mol 0.001 mol 1.00 mol
0.999 mol 0 1.001 mol
1.8 x 10-4 (1.001)
[H = —18 x 10-4 M, pH = 3.74
(0.999)
(In a buffer calculation, volumes cancel and we can substitute moles
directly into the Ka expression.)
Buffer B: HCOO' HC1 —> HCOOH + CI -

0.010 mol 0.001 mol 0.010 mol
0.009 mol 0 0.011 mol
535
Aqueous Equilibria
1.8 x 10 (0.011)
[H+] - = 2.2 x 10_4 M, pH = 3.66

(0.009)
(d) Buffer A: 1.00 M HC1 x 0.010 L = 0.010 mol H+ added
mol HCOOH = 1.00 + 0.010 = 1.01 mol
mol HC00- = 1.00 - 0.010 = 0.99 mol
] 1.8 x 10 (1.01)
[H+ = - 1.8 x 10_4M, pH = 3.74
(0.99)
Buffer B: mol HCOOH = 0.010 + 0.010 = 0.020 mol = 0.020 M
mol HC00-= 0.010 - 0.010 = 0.000 mol
The solution is no longer a buffer; the only source of HCOO - is the dissociation of
HCOOH.
Ka =
[H+ ] [C00-] x2
[HCOOH] - (0.020 - x) M
The extent of ionization is greater than 5%; from the quadratic formula, x = [H+]=
1.8 x 10-3, pH = 2.74.
(e) Adding 10 mL of 1.00 M HC1 to buffer B exceeded its capacity, while the pH of
buffer A was unaffected. This is quantitative confirmation that buffer A has a
significantly greater capacity than buffer B. In fact, 1.0 L of 1.0 M HC1 would be
required to exceed the capacity of buffer A. Buffer A, with 100 times more HCOOH
and HC00- has 100 times the capacity of buffer B.
17.87
0.15 mol CH3COOH

1 L soln
x 0.750 L = 0.1125 = 0.11 mol CH3COOH
1 g gl acetic acid x 1.00 mL gl acetic acid
0.1125 mol CH3COOH x 60.05 g CH3COOH x

1 mol CH3COOH 0.99 g CH3COOH 1.05 g gl acetic acid
= 6.5 mL glacial acetic acid
At pH 4.50, [IP] =10-4.50 = 3.16 x 10-5 = 3.2 x 10-5M; this is small compared to
0.15 M CH3COOH.
Ka = (3.16 x 10-5) [CH3C00-] 1.8 x

0.15
0.0854 mol CH3COONa
10-5; [CH3C00-] = 0.0854 = 0.085 M
82.03 g CH3COONa
x 0.750 L x 5.253 = 5.25 g CH3COONa

1 L soln 1 mol CH3COONa
17.88 (a) For a monoprotic acid (one per mole of acid), at the equivalence point
moles
OH- added = moles H+ originally present
MB x VB = g acid/molar mass
536
Aqueous .Equilibria
MM= g acid
0.2140 g
- 82.21 = 82.2 mol
MB x VB
0.0950 M x 0.0274 L
0.2140g
gi
(b) initial mol HA = = 2.603 x 10-3 = 2.60 x 10-3 mol HA
82.21 g/mol
mol OH- added to pH 6.50 = 0.0950 M x 0.0150 L = 1.425 x 10 -3
= 1.43 x 10-3 mol OH-
HA(aq) + NaOH(aq) -> NaA(aq) + H2O

before rx 2.603 x 10-3 mol 1.425 x 10-3 mol 0
change -1.425 x 10-3 mol -1.425 x 10-3 mol +1.425 x 10-3 mol
1.178 x 10-3 mol
[HA] =
[Al=
0.0400 L
1.425 x 10-3 mol

0.0400 L
= 0.02945 = 0.0295 M
= 0.03563 = 0.0356 M; [HI] = 10-6'5° = 3.162 x 10-7
= 3.2 x 10-7 M
The mixture after reaction (a buffer) can be described by the acid dissociation
equilibrium.
HA(aq) H+ (aq) A- (aq)
initial 0.0295 M 0 0.0356 M
equil (0.0295 - 3.2 x 10-7M) 3.2 x 10-7M (0.0356 + 3.2 x 10-7) M

(3.162 x 10-7) (0.03563)
Ka = [HI] [A-] - 3.8 x 10-7
[HA] (0.02945)
(Although we have carried 3 figures through the calculation to avoid rounding
errors, the data dictate an answer with 2 significant figures.)
17.89 (a) For a monoprotic acid (one 1-1+ per mole of acid), at the equivalence
point moles
OH- added = moles 1-1+ originally present
0.1687 g
MM - g acid - 94. = 94.6 mol
MB x VB 0.1150M x 0.0155E 642 gi
0.1687g
(b) initial mol HA = 642 w =1.783 x 10-3 =1.78 x 10-3 mol HA
94. mol
mol OH- added to pH 2.85 = 0.1150 M x 0.00725 L = 8.338 x 10 -4
= 8.34 x 10-4 mol OH-
537
Aqueous Equilibria
HA(aq)
before rx 1.783 x 10-3 mol
change -0.834 x 10-3 mol
after rx 0.949 x 10-3 mol
NaOH(aq) —> NaA(aq) + H2O
0.834 x 10-3 mol 0

-0.834 x 10-3 mol 0.834 x 10-3 mol
0 0.834 x 10-3 mol
[HA]. 9.49 x 10-4 mot= 0.02919 = 0.0292 M

0.0325 L
]
[A-
- 834 x 10-4 mot= 0.02565 = 0.0257 M

0.0325 L
[H+ ] =10-2'55 =1.413 x 10-3 =1.4 x 10-3
The mixture after reaction (a buffer) can be described by the acid dissociation
equilibrium.
HA(aq) 111-(aq)
initial 0.0292 M 0
equil (0.0292 - 1.4 x 10-3M) 1.4 x 10-3M
[conj. base]
+ A- (aq)
0.0257 M
(0.0257 + 1.4 x 10-3) M
[A-]
From Equation [17.9], pH = pKa +log = pKa +log

[conj. acid] [HA-] •
If [A-]/[HA] =1, log(1) = 0 and pH = pKa of the weak add being titrated.
17.91
The reaction involved is HA(aq) + OH- (aq) A- (aq) + H20(1). We thus have
0.080 mol A- and 0.12 mol HA in a total volume of 1.0 L, so the "initial" molarities
of
A- and HA are 0.080 M and 0.12 M, respectively. The weak acid equilibrium of
interest
is
HA(aq) 1-1+ (aq) + A - (aq)
(a) Ka = [H+1 [Al ; [H+ ] =10-43° =1.58 x 10-5 =1.6 x 10-5 M
[HA]
Assuming [H+] is small compared to [HA] and [A -],
538
Aqueous Equilibria
10-5) (0.080)
Ka N(1.58 x = 1.06 x 10-5 = 1.1 x 10-5, pKa = 4.98

(0.12)
(b) At pH = 5.00, [H+] = 1.0 x 10-5M. Let b = extra moles NaOH.
[HA] = 0.12 - b, = 0.080 + b
(1.0 x 10-5) (0.080+b)
1.06 x 10-5 ,2.06 x 10-5 b = 4.72 x 10-;
(0.12 -b)
b = 0.023 mol NaOH
17.92 Assume that H3PO4 will react with NaOH in a stepwise fashion: (This is not
unreasonable, since the three Ka values for H3PO4 are significantly different.)
H3PO4(aq) + NaOH(aq) H2PO4-(aq) + Na+ (aq) + H20(1)
before 0.20 mol 0.30 mol 0 mol
after 0 mol 0.10 mol 0.20 mol
H2PO4-(aq) + NaOH(aq) -4 HPO4- (aq) + Na' (aq) H200)
before 0.20 mol 0.10 mol 0.25 mol
after 0.10 mol 0 0.35 mol
Thus, after all NaOH has reacted, the resulting 1.00 L solution is a buffer
containing
0.10 mol H2PO4- and 0.35 mol HP042-. H2PO4-(aq) = H+ (aq) + HP042-(aq)
2- I [H+] ; [Fr] 6.2 x 10-8 (0.10 M)
17.93
Ka = 6.2 x 10-8 = [HP° - 1.77 x 10-8 = 1.8 x 10-8 M;

[H2P04- ] 0.35 M
pH = 7.75
The pH of a buffer system is centered around pKa for the conjugate acid
component. For a diprotic acid, two conjugate acid/conjugate base pairs are
possible.
H2X(aq) = H+ (aq) + HX- (aq); Kai = 2 x 10-2; pKai = 1.70
HX-(aq) = H+ (aq) + X 2-(aq); Ka2 = 5.0 x 10-7; pKa2 = 630
Clearly HX- / X2- is the more appropriate combination for preparing a buffer with
pH = 6.50. The [H+] in this buffer = 10-6.50 = 3.16 x 10-7 = 3.2 x 10-7 M. Using the
Ka2 expression to calculate the [X21 / [FIX -] ratio:
[H +][X2-] Ka2 [X2-] 5.0 x 10-7
K2 =a - = 1.58=1.6
[lX -] [HI] [HX-] 3.16 x 10-7
Since X2- and FIX- are present in the same solution, the ratio of concentrations is
also a ratio of moles.
[X2-] mol X2- /L soln mol X2-

[HX-] mol HX- soln = mol HX-
-1.58; mol X2- = (1.58) mol HX-

In the 1.0 L of 1.0 M H2X, there is 1.0 mol of material containing X2- .
539
1 7 Additional Aspects of Solutions to Exercises
Aqueous Equilibria
Thus, mol HX- + 1.58 (mol HX-) = 1.0 mol. 2.58 (mol HX-) = 1.0;
mol HX- = 1.0 / 2.58 = 0.39 mol HX-; mol X2- = 1.0 - 0.39 = 0.61 mol X2-.
Thus enough 1.0 M NaOH must be added to produce 0.39 mol HX - and 0.61 mol
X2-.
Considering the neutralization in a step-wise fashion (see discussion of titration of
polyprotic acids in Section 17.3).
H 2X(aq) + NaOH(aq) HX-(aq) F120(1)
before 1.0 mol 1 mol 0
after 0 0 1.0 mol
HX (aq) + NaOH(aq) +- X2-(aq) + H20(1)
before 1.0 0.61
change -0.61 -0.61 +0.61
after 0.39 0 0.61
Starting with 1.0 mol of H2X, 1.0 mol of NaOH is added to completely convert it to
1.0 mol of HX-. Of that 1.0 mol of HX-, 0.61 mol must be converted to 0.61 mol X2-.
The total moles of NaOH added is (1.00 + 0.61) = 1.61 mol NaOH.
L NaOH = mol NaOH - 1.61 mol = 1.6 L of 1.0 M NaOH

M NaOH 1.0 M
17.94 CH3CH(OH)C00- will be formed by reaction CH3CH(OH)COOH with NaOH.

0.1000 M x 0.02500 L = 2.500 x 10-3 mol CH3CH(OH)COOH; b = mol NaOH
needed
CH3CH(OH)COOH +
initial 2.500 x 10-3 mol

rx -b mol
after rx (2.500 x 103 - b) mol
Ka - [W] [CH3CH(OH)C°Cr]; Ka
[CH3CH(OH)COOH]
NaOH +- CH3CH(OH)C00- + H2O + Na+
b mol
-b mol +b mol
0 b mol
=1.4 x 10-4; [H+] = 10-PH =10-3.75 =1.778 x 10" =1.8 x 10-4M
Since solution volume is the same for reaction CH3CH(OH)COOH and

CH3CH(OH)C00-, we can use moles in the equation for [H+].
_A
Ka = 1.4 x 10 -
1.778 x
(2.500 x
10-4 (b)
10-3 - b)
3 - b) = b, 1.969 x 10-3 = 1.7874 b,

b = 1.10 x 10-3= 1.1 x 10-3 mol OH-
(The precision of Ka dictates that the result has 2 sig figs.)
Substituting this result into the Ka expression gives [H+] = 1.8 x 10 -4. This checks
and confirms our result. Calculate volume NaOH required from M = mol/L.
1.10 x 10-3 mol OH- x
1 L 1
1.000 mol x 1 x 10-6 L
540
103 µLL (1.1 mL)

-1.1 x
Aqueous Equilibria
17.95 (a) H+ (aq) + HCO3-(aq) H2 CO3 (aq)
H2 0(1) + CO2 (g)
A person breathing normally exhales CO2(g). Rapid breathing causes excess

CO2(g) to be removed from the blood. By LeChatelier's principle, this causes both
equilibria above to shift right, reducing [H+] in the blood and raising blood pH.
(b) Breathing in a paper bag traps the exhaled CO2; the gas in the bag contains
more
CO2 than ambient air. When a person inhales gas from the bag, a greater amount
(partial pressure) of CO2(g) in the lungs shifts the equilibria left, incr easing [H+]
and lowering blood pH.
17.96 (a) CdS: 8.0 x 10-28; CuS: 6 x 10-37 CdS has greater molar solubility.
(b) PbCO3: 7.4 x 10-14; BaCrO4: 2.1 x 10-10 BaCrO4 has greater molar solubility.
(c) Since the stoichiometry of the two complexes is not the same, values can't be
compared directly; molar solubilities must be calculated from Kap values.
Ni(OH)2: Kap = 6.0 x 10-16 = [Ni21[0H-] 2; [Ni2] = x, [OH-] = 2x
6.0 x 10-16= (x)(2x)2 = 4x3; x = 5.3 x 10-6M Ni2+
Note that [OH-] from the autoionization of water is less than 1% of [OH-] from
Ni(OH)2 and can be neglected.
NiCO3: Kap = 1.3 x 10-7= [Ni21[C0321; [Ni21 = [C032-] = x
1.3 x 10-7= x2; x = 3.6 x 10-4M NO+
NiCO3 has greater molar solubility than Ni(OH) 2, but the values are much closer
than expected from inspection of Kap values alone.
(d) Again, molar solubilities must be calculated for comparison.
Ag2SO4: Kap = 1.5 x 10-'5= [Ag12[S042-]; [S0421 = x, [Ag+] = 2x
1.5 x 10-5= (2x)2(x) = 4x3; x = 1.6 x 10-2M 5042-

AgI: Kap = 8.3 x 10-17 = [Ag+]11-1; [AO = [I-] = x
8.3 x 10-17= x2; x = 9.1 x 10-9M Ag+
Ag2SO4 has greater molar solubility than AgI.
17.97 (a) Kap = 4.5 x 10-9 = [Ca21[C032-]; s = [Ca21 = [C032-]

s2 = 4.5 x 10-9, s = 6.708 x 10-5 = 6.7 x 10-5
(b) CaCO3(s) Ca2+ (aq) + C032- (aq) Kap
co32-(aq) + H20(1) HCO3- (aq) + OH- (aq) Kb
Kb = Kw/Ka for HCO3
541
Aqueous Equilibria
Ksp X KW
4.5x10 x 1x10-14
K =Ksp x Kb - - = 8.036 x 10-13 = 8.0 x 10-13

Ka for HCO3- 5.6 x 10-11
(c) K = 8.036 x 10-13 = [Ca2+][C032-][0H-] = s3; s = 9.297 x 10-5 = 9.3 x 10-5 M
[OH-] = s = 9.297 x 10-5 M; p0H = 4.03165 = 4.03; pH = 14 - 4.03 = 9.97
(d) pH = 8.2, p0H = 14 - 8.2 = 5.8. [OH-] = 10-5.8 = 1.585 x 10-6 = 2 x 10-6 M
8.036 x 10-13 =s2( 1.585 x 10-6), s= 7.121 x 10-4 = 7 x 10-4 M
(e) pH = 7.5, p0H = 14 - 7.5 = 6.5. [OH-] = 10-6.5 = 3.162 x 10-7 = 3 x 10-7 M
8.036 x 10-13 = s2( 3.162 x 10-7), s = 1.549 x 10-3 = 2 x 10-3 M
The drop in pH from 8.2 to 7.5 approximately doubles (from 7 x 10 -4 M to
15 x 10-4 M) the molar solubility of CaCO3(s).
17.98 (a) Hydroxyapatite: Ksp = [Ca2-15[P04313[0H-]

Fluoroapatite: Ksp = [Ca2-15[P04313[F-]
(b) For each mole of apatite dissolved, one mole of OH - or F- is formed. Express
molar solubility, s, in terms of [OW] and [F-].
Hydroxyapatite: [OW] = s, [Ca2+] = 5s, [P043 -] = 3s Ksp = 6.8 x 10-22 = (5s)5(3s)3
(s) = 84,375 s9
s9= 8.059 x 10-32= 8.1 x 10-32.
Use logs to find s. s = 3.509 x 10-4 = 3.5 x 10-4M Ca5(PO4)30H. Fluoroapatite: [F-
] = s, [Call = 5s, [P043-] = 3s
Ksp = 1.0 x 10-68 = (5s)5(3s)3 (s) = 84,375 s9
s9=1.185 x 10-65= 1.2 x 10-65; s = 6.109 x 10-8 = 6.1 x 10-8M Ca5(PO4)3F
17.99 Cr(OH)3(s) Cr3+ (aq) + 30H- (aq) Ksp

Cr3+ (aq) + 40H- (aq) ;--". Cr (OH)4- (aq) Kf
Cr(OH)3(s) + OH-(aq) ;--". Cr (OH)4-(aq)

K = Ksp x Kf = (6.7 x 10-31)(8 x 1029) = 0.536 = 0.5
K = [Cr(OH)41
_ ; p0H = 14 - pH = 14 - 10.0 = 4.0; [OH -] = 1 x 10-4M
[OH-]
[Cr(OH)4-] = K x [OH-] = 0.536(1 x 10-4) = 5.36 x 10-5 = 5 x 10-5M
(The Ksp value for Cr(OH)3 listed in Appendix D is different from the value given in
this exercise.)
17.100 Analyze/Plan. Calculate the solubility of Mg(OH)2 in 0.50 M NH4C1. Find

Kw for
Mg(OH)2 in Appendix D. NH4+ is a weak acid, which will increase the solubility of
Mg(OH)2. Combine the various interacting equil ibibria to obtain an overall reaction.
Calculate K for this reaction and use it to calculate solubility (s) for Mg(OH)2 in
0.50 M NH4C1. Solve.
542
1 7 Additional Aspects of
Aqueous Equilibria
Mg(OH)2(s)
2NH4+(aq)
2H+(aq) + 20H-(aq)
Mg2+(aq) + 2 OH-(aq) Kap
2NH(aq) + 2H+(aq) Ka
2H20(1) 1/Kw
Mg(OH)2(s) + 2NH4+(aq) + 2H+(aq) + 20H-(aq) -=Mg2+(aq) + 2NH3(aq)

+ 20H- (aq) + 2H+(aq) + 2H20(1)
Mg(OH)2(s) + 2NH4*(aq) Mg2+(aq) + 2NH3(aq) + 2H20(1)
K = [Mg2+.1 [NH3]2
[NH412
Ka for NH4* =
Kap X Ka2
Kw
Kw Ka 1
K= Ks F)Ca2Kw2
Kb for NH3 Kw Kb
K sp 1.8 X 10-11
--b2 - 5.556 x 10-2 = 5.6 x 10-2
K (1.8 x 10-5)2
Let [Mg2+] = s, [NH3] = 2s, [NH4+] = 0.50 - 2s
K = 5.6 x 10-2 . [Mg2+][NH312

[NH4*
(2s)2 4s3
(0.5 - 2s)2 = 0.25 - 2s + 4s2
5.6 x 10-2(0.25 - 2s + 4s2) = 4s3; 4s3 - 0.222s2 + 0.111s - 1.39 x 10-2 = 0
Clearly, 2s is not small relative to 0.50. Solving the third -order equation, s =
0.1054 =
0.11 M. The solubility of Mg(OH)2 in 0.50 M NH4C1 is 0.11 mol/L. Check.
Substitute s = 0.1054 into the K expression.
K -
4(0.1054)3
[0.50 - 2(0.1054)12
- 5.6 x 10-2
The solubility and K value are consistent, to the precision of the Icp and Kb values.
17.101 Ksp = [Ba2+1[Mn04-]2 = 2.5 x 10-1°

[Mn04-]2 = 2.5 x 10-10 / 2.0 x 10-8 = 0.0125; [Mn04-] = 0.0125 = 0.11 M
17.102 [Ca21[C032-] = 4.5 x 10-9; [Fe21[C032-] = 2.1 x 10-11
Since [C032-1 is the same for both equilibria:
_4.5 x 10-9 2.1 x 10-11 [Ca2+ . 4.5 x 10

[co32-] rearranging -9 - 214 = 2.1 x 102
[Ca2+] [Fe2+] ; [Fe 2+] 2.1 x 10-11
17.103 PbSO4(s) Pb2+(aq) + 5047-(aq); Ksp = 6.3 x 10-7 = [Pb21 [93421
SrSO4(s) Sr2+(aq) + S042-(acj); Ksp = 3.2 x 10-7 = [Sr21 [5042-]
Let x = [Pb2+], y = [5/.21, x + y = [SO4 21
543
Aqueous Equilibria
x(x + y) = 6.3 x 10-7 x

, =1.9688 = 2.0; x =1.969 y = 2.0 y
y(x + y) 3.2 x 10-' ;
y(1.969 y+y) = 3.2 x 10-7; 2.969 y2 = 3.2 x 10-7; y = 3.283 x 10-4 = 3.3 x 10-4
x= 1.969 y; x = 1.969(3.283 x 10-4) = 6.464 x 10-4 = 6.5 x 10-4
[Pb2+] = 6.5 x 10-4M, [Sr2+] = 3.3 x 10-4M, [S042-] = (3.283 + 6.464) x 10-4 = 9.7
x 10-4M
17.104
MgC204(s) Mg2+(aq) + C2042-(aq)
K5,, = [Mg2+][C2042-] = 8.6 x 10-5
If [Mg2+] is to be 3.0 x 10-2M, [C20421 = 8.6 x 10-5/3.0 x 10-2= 2.87 x 10-3= 2.9 x
10-3M
The oxalate ion undergoes hydrolysis:
C2042-(aq) H20(1) HC204-(aq) + OH (aq)

[HC204-][0H-]
Kb =
[C2042
=]
=1.0 x 10-14 / 6.4 x 10-3 = 1.56 x 10-10 =1.6 x 10-1°
[Mg2+] = 3.0 x 10-2M, [C20421 = 2.87 x 10-3= 2.9 x 10-3M
[HC204-] = (3.0 x 10-2- 2.87 x 10-3)M = 2.71 x 10-2 = 2.7 x 10-2M
[C2042-]
[OW ] =1.56 x 10-1° x
[HC204-]
i n
-1.56 x 10-- x
(2.87 x 10-3)
, =1.652 x 10-11
(2.71 x 10-)
[OH-] = 1.7 x 10-11M; p0H = 10.78, pH = 3.22
17.105 The student failed to account for the hydrolysis of the As043 - ion. If there
were no
hydrolysis, [Mg2+] would indeed be 1.5 times that of [As043 -]. However, as the
reaction
As043-(aq) + H20(1) HAs042-(aq) + OH- (aq) proceeds, the ion product
[Mg213[As04312 falls below the value for Ku,. More Mg3(As04)2 dissolves, more
hydrolysis occurs, and so on, until an equilibrium is reached. At this point [Mg2+] in
solution is much greater than 1.5 times free [As0431. However, it is exactly 1.5
times the total concentration of all arsenic -containing species. That is,
[Mg2+] = 1.5 ([As043-] + [HAs0421 [112As04-] + [H3AsO4])
17.106 Zn(OH)2(s) Zn2+ (aq) + 20H-(aq) KSp = 3.0 x 1046
Zn2+ (aq) + 40H-(aq) Zn(OH)42-(a4) Kf = 4.6 x 1017
544
Aqueous Equilibria
17.107 (a) Cd(OH)2(s) Cd2+(aq) + 20H-(aq); K = 2.5 x 1044 = [Cd2+[[ OH-]2.

[Cd2+] = S; [ OH-] = 2s; Ksp = 2.5 x 10-14 = 4s3. s = 1.8 x 10-5 M.
(b) Cd(OH)2 (s) Cd2+ (aq) + 20H-(aq) Km, = 2.5 x 10-14

Cd2+ (aq) + 4Br(aq) CdBr42- (aq) Kf = 5 x 103
Cd(OH)2(s) + 4Br(aq) CdBr42-(aq) + 20H- (aq) K
K = X Kf = (2.5 x 10-14)( 5 x 103) = 1.25 x 10-1° = 1 x10-10

The desired molar solubility of Cd(OH)2 is 1.0 x 10 -3. Assume all soluble Cd2+ is
present as CdBr42-. [CdBr42-] = 1.0 x 10-3; [OH-] = 2(1.0 x 10-3) = 2.0 x
Let c = initial [NaBr] = initial [Br]; [Br] at equilibrium = c - 4(1.0 x 10-3) = (c - 4.0 x
10-3).
K = 1.25 x 10-10 _ [CdBr1-][0H-]2 = (1.0 x 10-3)(2.0 x 10-3)2

[Br-]4 (c - 4.0 x 10-3)4
Assume c is large relative to 4.0 x 10-3.

(1.25 x 10-1°)c4 = 4.0 x 10-9; c = (32)1/4 = 2.378 = 2 M. The approximation is
valid.
4.0 x leis about 0.2% of 2 M. Check this result in the equilibrium expression.
)(2.0 x 10-3)2
K - (1.0 x10-3 =1.26 x 10-10. Our calculations are consistent.
(2.378 - 4.0 x 10-3)4
Integrative Exercises
17.108 (a) Complete ionic (CHO2- = HC00-)

H+ (aq) + Q- (aq)+ Na+ (aq) + HC00-(aq) -, HCOOH(aq) + Na+ (aq) + Q-(aq)
Na+ and Cl- are spectator ions.
Net ionic: H+ (aq) + HC00-(aq) HCOOH(aq)
(b) The net ionic equation in part (a) is the reverse of the dissociation of HCOOH.
1 1
K= = - 5.55 x 103 = 5.6 x 103
K. 1.8 x 10-
(c) For Na+ and Cl-, this is just a dilution problem.
M1V1 = M2V2; V2 is 50.0 mL + 50.0 mL = 100.0 mL
0.15 M x 50.0 mL 0.15 M x 50.0 mL
Cl- = 0.075 M; Na+ : = 0.075 M
100.0 mL 100.0 mL
H+ and HC00- react to form HCOOH. Since K >> 1, the reaction essentially goes to
completion.
545
Aqueous Equilibria
0.15 M x 0.0500 mL = 7.5 x 10-3 mol H+

0.15 M x 0.0500 mL = 7.5 x 10-3 mol HC00-
= 7.5 x 10-3 mol HCOOH
Solve the weak acid problem to determine [Hl, [HC00 -] and [HCOOH] at
equilibrium.
Ka = [H+] [HC°°-]; = [HC00-] = x M; [HCOOH] - (7.5 x 10-3 -x) mol

[HCOOH] 0.100 L
= (0.075 - x) M
3(2
X2
1.8 x 10-4 =
(0.075 - x)
; x = 3.7 x 10-3 M H+ and HC00-

0.075
[HCOOH] = (0.075 - 0.0037) = 0.071 M

[H+]
[HCOOH]
x 100 =
3.7 x 10-3
0.075
x 100 = 4.9% dissociation
In summary:
[Na] = [C1-] = 0.075 M, [HCOOH] = 0.071 M, = [HCOO -] = 0.0037 M
17.109 (a) For a monoprotic acid (one per mole of acid), at the equivalence point
moles OH- added = moles H+ originally present
g acid 0.1044g
= = 94. = 94.5 g/mol
MM MB X VB 0.0500 M x 0.02210 L 48
(b) 11.05 mL is exactly half -way to the equivalence point (22.10 mL). When half of
the unknown acid is neutralized, [HA] = [W] = Ka and pH = pKa.
Ka = 10-4.89 = 1.3 x 10-5
(c) From Appendix D, Table D.1, adds with Ka values close to 1.3 x 10 -5 are
name Ka formula molar mass
propionic 1.3 x 10-5 C2H5COOH 74.1
butanoic 1.5 x 10-5 C3H7COOH 88.1
acetic 1.8 x 10-5 CH3COOH 60.1
hydroazoic 1.9 x 10-5 HN 3 43.0
Of these, butanoic has the closest match for Ka and molar mass, but the
agreement is not good.
546
Aqueous Equilibria
1 atm
7.5 L K - mol
17.110 n = PV = 735 torr x x x 06 tm = 0.300 = 0.30 mol NH3

RT 760 torr 295 K 0.082 L - a
0.40 M x 0.50 L= 0.20 mol HC1
HC1(aq) + NH3(g) -* NH4+ (aq) + Ct(aq)

Before 0.20 mol 0.30 mol
after 0 0.10 mol 0.20 mol 0.20 mol
The solution will be a buffer because of the substantial con centrations of NH3 and
NH4+ present. Use Ka for NH4+ to describe the equilibrium.
equil.
Ka =
NH4+ (aq)
0.20 - x
1.0 x 10-14
1.8 x 10-5
NH3(aq) + H+ (aq)
0.10 + x x
- 5.56 x 10-1° = 5.6 x 10-1°; K
Ka [NH4+] = [NH3] [H+]

a [NH41 [NH3]
Since this expression contains a ratio of concentrations, volume will cancel and we
can
substitute moles directly. Assume x is small compared to 0.10 and 0.20.
5.56 x 104° (0.20)

[H+] -
(0.10)
=1.111 x 10-9 =1.1 x 10-9 M, pH = 8.95
17.111 Calculate the initial M of aspirin in the stomach and solve the equilibrium
problem to
find equilibrium concentrations of C8H7O2COOH and C8H702C00 -. At pH = 2,
[H+] = 1 x 10-2.
1 g 1 mol C8H7O2COOH x 1
325 mg x 2 tablets x
tablet 1000 mg x180.2 g C8H7O2COOH
M■bb.
■■•■
3.61 x 10-3 = 4 x 10-3 M
1 L
Cs H702COOH(aq)
initial
3.61 x 10-3M
equil (3.61 x 10-3 - x) M
5 = [H+] [C8H702C00-] -
Ka = 3 x 10-
[C8H7O2COOH]
C8F1702C00- + H+ (aq)
0 1 x 10-2M
x M (1 x 10-2+ x)M
(0.01+x) (x) 0.01 x

(3.61 x 10-3 -x) 3.61 x 10-3
x = [C8H702C00-] = 1.08 x 10-5= 1 x 10-5M
% ionization = 1.08 x 10-5 M C8H702C00-x 100 = 0.3%

3.61 x 10-3 M C8H7O2COOH
(% ionization is small, so the approximation was valid.) % aspirin mo lecules =
100.0% - 0.3% = 99.7% molecules
547
Aqueous Equilibria
17.112 According to Equation [13.4], Sg = kPg
2 mol 0.034 mol

Sc02 = 3.1 x 10- x 1.10 atm = 0.0341 = - 0.034 M CO2
L - atm
CO2(g) + H20(1) H2CO3(aq); 0.0341
M CO2 = 0.0341 M H2CO3
Consider the stepwise dissociation of H2CO3(aq).
H2CO3(aq)
initial 0.0341 M
equil. (0.0341-x) M
[H+ ][HCO3-]
x2
1-1*(aq) HCO 3- (aq)
0 0
2
x
r`al. =
[H2CO3] (0.0341-x)
4.3 x 10-7
0.0341
x2 = 1.47 x 10-8; x = 1.2 x 10-4 M F1+; pH = 3.92
Ka2 = 5.6 x 10-11; assume the second ionization does not contribute significantly
to [111.
17.113 Ca(OH)2(aq) + 2HC1(aq) CaC12(aq) + 2H20
mmol = M x mL = 0.0983 M x 11.23 mL = 1.1039 = 1.10 mmo1HC1
mmol Ca(OH) 2 = mmol HC1/2 = 1.1039/2 = 0.55195 = 0.552 mmol Ca(OH) 2
0.55195 mmol
[Ca2+] = = 0.01104 = 0.0110 M
50.00 mL
[OH-] = 2[Ca21 = 0.02208 = 0.0221 M
Ks p = [Ca2+][0F1-] 2 = (0.01104)(0.02208)2 = 5.38 x 10-6
The value in Appendix D is 6.5 x 10-6, a difference of 17%. Since a change in

temperature does change the value of an equilibrium constant, the solution may not
have been kept at 25 °C. It is also possible that experimental errors led to the
difference
in Ks
p values.
11 21 torr 1 atm K -mol
17.114 11 = MRT,M= =
RT 298K
x x
760 torr 0.08206 L- atm
=1.13x10-3=1.1x10-3M
SrS0 4 (S) ■-.' Sr 2 +(aq) + S042-(aq); Ks
p =
[Sr 21 [S0421
The total particle concentration is 1.13 x 10-3 M. Each mole of SrSO4 that
dissolves
produces 2 mol of ions, so [Sr2+] = [S0421 = 1.13 x 10 -3 M/2 = 5.65 x 10-4 = 5.7 x
10-4 M
Ksp = (5.65 x 10-4)2 = 3.2 x 10-7
17.115 For very dilute aqueous solutions, assume the solution density is 1 g/mL.
g solute 1 x 104 g solute u g solute

PP° - g
10- g solution 1 x 103 g solution - L solution
Aqueous Equilibria
(a) KSp = [Agl[C1-] = 1.8 x 10-10; [Ag+] = (1.8 x 10-19)1/2= 1.34 x 10-5= 1.3 x 10-
5M
1.34 x mol Ag+x 107.9 g Ag+ x 1µg 1.4 x 103 1.1g Ag+
L lmol Ag+ 1 x 10-8 g
=1.4 x 103 ppb =1.4 ppm
(b) KSp=[Ag+][Br-]=5.0x10-13;[Ag+]=(5.0x10-13)1/2=7.07x10 -7= 7.1x10-7M
7.07 x 10-7 mol Ag+ x 107.9 g Ag+
x 1µg = 76ppb
L 1 mol Ag+ 1 x 10— g
(c) KSp = = 8.3 x 10-17; [Agl = (8.3 x 10-17)1/2 = 9.11 x 10-9= 9.1 x 10-9M
9.11 x 10-9 mol Ag+ x 107.9 g Ag+
x 1µg = 0.98 ppb
L lmol Ag+ 1 x 10— g
AgBr(s) would maintain [Agl in the correct range.
17.116 To determine precipitation conditions, we must know Ksp for CaF2(s) and
calculate Q
under the specified conditions. Ks p = 3.9 x 10 -'1= [Ca21[F12
Ka2+1 and [F-]. The term 1 ppb means 1 part per billion or 1 g solute per billion g
solution. Assume that the density of this very dilute solution i s the density of water.
1 g solute x
1 ppb
1 x 109 g solution 1 x 104 gsolute x
1 g solution 1 x 103 mL 1 x 10-6g solute

1 mL solution 1 L 1 L solution
1µg _1 g/1 L
1L solution 1 x 10— g
1µg = 8 ggCa2+ 8 x 10-8 g Ca2+ 1 mol Ca2+
8 ppb Ca2+ x
1L 1L 1L 40g
1 pg F- 1 x 10-6 g F-x 1 mo1F-=
= 2 x 10-7 M Ca2+
1 ppb F- x 1ag =
1L
]
5 x.10-8 M F-
1L 1L
19.0 g
Q = [Ca21[F 2 = (2 x 10-7)(5 x 10-8)2 = 5 x 10-22

5 x 10-22 < 3.9 x 10-11, Q < Ksp, no CaF2 will precipitate
549
▪▪
18
Chemistry
of the
Environment
Visualizing Concepts
18.1 Analyze. Given that one mole of an ideal gas at 1 atm and 298 K occupies
22.4 L, is the
volume of one mole of ideal gas in the middle of the stratosphere greater than,
equal to, or less than 22.4 L?
Plan. Consider the relationship between pressure, temperature, and volume of an
ideal gas. Use Figure 18.1 to estimate the pressure and temperature in the middle
of the stratosphere, and compare the two sets of temperature and pressure.
Solve. According to the ideal gas law, PV = nRT, so V = nRT/P. Since n and R are
constant for this exercise, V is proportional to T/P.
(a) The stratosphere ranges from 10 to 50 km, so the middle is at approximately
30 km. At this altitude, T 230 K, P 40 torr (from Figure 18.1). Since we are
comparing T/P ratios, either atm or torr can be used as pressure units; we will use
torr.
At sea level: T/P = 298 K/760 torr = 0.39 At 30 km T/P = 230 K/40 torr = 5.75
The proportionality constant (T/P) is much greater at 3 0 km than sea level, so the
volume of 1 mol of an ideal gas is greater at this altitude. The decrease in
temperature at 30 km is more than offset by the substantial decrease in pressure.
(b) Volume is proportional to T/P, not simply T. The relative volumes of one mole of
an ideal gas at 50 km and 85 km depend on the temperature and pressure at the
two altitudes. From Figure 18.1,
50 km: T 270 K, P z 20 torr, T/P = 270 K/20 torr = 13.5
85 km: T 190 K, P < 0.01 torr, T/P = 190 K/0.01 torr = 19,000
Again, the slightly lower temperature at 85 km is more than offset by a much lower
pressure. One mole of an ideal gas will occupy a much larger volume at
85 km than 50 km.
(c) Gases behave most ideally at high temperature and low pressure. Pressure is
minimum and temperature is high in the thermosphere. The stratopause (the
boundary between the stratosphere and mesosphere) and the troposphere at low
altitude are other regions with temperature maxima and relatively low pressures.
18.2 Molecules in the upper atmosphere tend to have multiple bonds because they
have
sufficiently high bond dissociation enthalpies (Table 8.4) to survive the incoming
high energy radiation from the sun. According to Table 8.4, for the same two
bonded atoms,
550
18 Chemistry of the Environment Solutions to Exercises
multiple bonds have higher bond dissociation enthalpies than single bonds.
Molecules with single bonds are likely to undergo photodissociation in the presence
of the high energy, short wavelength solar radiation present in the upper
atmosphere.
18.3 (a) A= troposphere, 0-10 km; B= stratosphere, 12-50 kin; C= mesosphere, 50-
85 km
(b) Ozone is a pollutant in the troposphere and filters UV radiation in the
stratosphere.
(c) Infrared radiation from Earth is most strongly reflected back in the troposphere.
(d) Assuming the "boundary" between the stratosphere and mesosphere is at 50
km,
only region C in the diagram is involved in an aurora borealis.
(e) The concentration of water vapor is greatest near Earth's surface in region A
and
decreases with altitude. Water's single bonds are susceptible to
photodissociation in regions B and C, so it's concentration is likely to be very low
in these regions. The relative concentration of CO2, with strong double bonds,
increases in regions B and C, because it is less susceptible to photodissociation.
18.4 Analyze. Given granite, marble, bronze, and other solid materials, what
observations
and measurements indicate whether the material is appropriate for an outdoor
sculpture? If the material changes (erodes) over time, what chemical processes are
responsible?
Plan. An appropriate material resists chemical and physical changes when exposed
to environmental conditions. An inappropriate material undergoes chemical
reactions with substances in the troposphere, degrading the structural strength of
the material
and the sculpture. Solve.
(a) The appearance and mass of the material upon environmental exposure are
both
indicators of chemical and physical changes. If the appearance and mass of the
material are unchanged after a period of time, the material is well -suited for the
sculpture because it is inert to chemical and physical changes. Changes in the
color or texture of the material's surface indicate that a chemical reaction has
occurred, because a different substance with different properties has formed. A
decrease in mass indicates that some of the material has been lost, either by
chemical reaction or physical change. An increase in mass indicates corrosion. If
the mass of the material is unchanged, it is probably inert to chemical and physical
environmental changes and suitable for sculpture.
(b) The two main chemical processes that lead to erosion are reaction with acid
rain
and corrosion or air oxidation, which is encouraged by acid conditions (see S ection
20.8).
Acid rain is primarily H2S03 and/or H2SO4, which reacts directly with carbonate
minerals such as marble and limestone. Acidic conditions created by acid rain
encourage corrosion of metals such as iron, steel, and bronze. Corrosion produces
metal oxides which may or may not cling to the surface of the material. If the
oxides are washed away, the material will lose mass after corrosion. Physical
erosion due to the effects of wind and rain on soft materials such as sandstone
also causes mass to decrease.
551
18.5 The Sun

18.6 Saltwater, freshwater and groundwater differ in salt content, location and
percentage of
Earth's total water.
Saltwater contains high concentrations of dissolved salts and solids and includes
the world ocean (97.2% of all water) and brackish or salty water (0.1% of all water)
in places such as the Great Salt Lake and the Chesapeake Bay. The world ocean
averages about
35 g of dissolved salts per kg of water, or 35, 000 ppm.
Freshwater (0.6% of all water on earth) refers to natural waters that have low
concentrations (less than 500 ppm) of dissolved salts and solids. Freshwater
indudes the waters of lakes, rivers, ponds, and streams.
Groundwater is freshwater that is under the soil. It resides in aquifers, porous rock
that holds water, and composes 20% of the world's freshwater.
18.7 CO2(g) dissolves in seawater to form H2CO3(aq). The basic pH of the ocean
encourages
ionization of H2CO3(aq) fo form HCO3-(aq) and C032-(aq). Under the correct
conditions, carbon is removed from the ocean as CaCO3(s) (sea shells, coral,
chalk cliffs). As carbon is removed, more CO2 (g) dissolves to maintain the balance
of complex and interacting add-base and precipitation equilibria.
18.8 Analyze/Plan. Explain how an ion-exchange column "softens" water. See the
Closer
Look box on "Water Softening" in Section 18.4.
Solve. The plastic beads in an ion-exchange column contain covalently bound
anionic groups such as R—COO- and R—S03-. These groups have Na+ cations
associated with them for charge balance. When "hard" water containing Ca2+ and
other divalent cations passes over the beads, the 2+ cations are attracted to the
anionic groups and Na+ is displaced. The higher charge on the divalent catio ns
leads to greater electrostatic attractions, which promote the cation exchange. The
"soft" water that comes out of the column contains two Na+ ions in place of each
divalent cation, mostly Ca2+ and Mg2+, that remains in the column associated with
the plastic beads.
18.9 The guiding principle of green chemistry is that "an ounce of prevention is
worth a
pound of cure." Processes should be designed to minimize or eliminate solvents
and waste, generate nontoxic waste, be energy efficient, employ renewable st arting
materials, and take advantage of catalysts that enable the use of safe and common
reagents.
18.10 Some of the missing CO2 is absorbed by "land plants" (vegetation other than
trees) and
incorporated into the soil. Soil is the largest land -based carbon reservoir. The
amount of carbon-storing capacity of soil is affected by erosion, soil fertility, and
other complex factors. For more details, search the internet for "carbon budget."
Earth's Atmosphere (section 18.1)
18.11 (a) The temperature profile of the atmosphere (Figure 18.1) is the basis of its
division
into regions. The center of each peak or trough in the temperature profile
corresponds to a new region.
552
(b) Troposphere, 0-12 km; stratosphere, 12-50 km; mesosphere, 50-85 km;
thermosphere, 85-110 km.
18.12 (a) Boundaries between regions of the atmosphere are at maxima and
minima (peaks
and valleys) in the atmospheric temperature profile. For example, in the
troposphere, temperature decreases with altitude, while in the stratosphere, it
increases with altitude. The temperature minimum is the tropopause boundary.
(b) From Figure 18.1, atmospheric pressure in the troposphere ranges from 760
torr
to 200 torr, while pressure in the st ratosphere ranges from 200 torr to 20 torr. Gas
density (g/L) is directly proportional to pressure. The much lower density of the
stratosphere means it has the smaller mass, despite having a larger volume than
the troposphere.
18.13 Analyze/Plan. Given 03 concentration in ppm, calculate partial pressure. Use
the
definition of ppm to get mol fraction 03. For gases mole fraction = pressure
fraction.
Use the ideal-gas law to find mol 03/L air and Avogadro's number to get
molecules/L.
0A41 mol 0
P03 = z03 x Patm ; 0.441 ppm 03 =
3 - 4.41 x
1 x 106 mol air
10-7 = Xo, Solve.
(a)
Poi = x03 x P_ atm = 4.41 x
PV
10-7 (0.67 atm) = 2.955 x 10-7 = 3.0 x

mol - K
10-7 atm
(b) n = = 2.955 x 10-7 atm x 1.0 L x

RT 298 K 0.08206 L - atm
molecules
- 1.208 x 10-8 = 1.2 x 10-8 mol 03
1.208 x 10_8 mol 03 x 6.022 x 1023 = 7.277 x 1015 = 7.3 x 1015 03 molecules
mol
18.14 PA, = XAr x Patin; PAr = 0.00934 (1.05 bar) = 0.009807 = 9.81x 10 -3 bar
105Pa 760 torr

PAr = 0.009807 bar x x = 73559 = 7.36 ton
bar 101,325 Pa
Pa), = Xco, x Pawn; Pco, = 0.000382 (1.05 bar) = 0.0004011 = 4.01 x 10 -4 bar
1300,
105Pa
= 0.0004011 bar x
bar
760 torr
x - 0.30085 = 0.301 torr
101,325 Pa
18.15 Analyze/Plan. Given CO concentration in ppm, calculate number of CO

molecules in
1.0 L air at given conditions. ppm CO x03 atm CO mol CO molecules CO.
Use the ideal gas law to change atm CO to mol CO, then Avogadro's number to get
molecules. Solve.
3.5 mol CO
3.5 ppm CO = - 3.5 x 10-6

1 x 10 mol air
Pco = Xco x Patin = 3.5 x 10-6 x 759 torr x
3.495 x 10-6 atm x 1.0 L
= Xco
1 atm
760 torr
mol -K
= 3.495 x 10-6 = 3.5 x 10-6 atm

nCO .P00V _ x
RT 295 K 0.08206 L - atm
6.022 x 1023 molecules
= 1.444 x 10-7 = 1.4 x 10-7mol CO
1.444 x 10-7 mol CO x = 8.695 x 1016 = 8.7 x 1016 molecules CO

mol
553

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17 ASPECTOS ADICIONALES

17.1 Analizar. Dados diagramas que muestran mezclas de equilibrio de HX y X -

17 Aspectos Adicionales de las Soluciones a los Ejercicios

17.4 Analizar/Planificar. Cuando se añade ácido fuerte a un tampón, reacciona con

(b) According to the Henderson-Hasselbach equation, pH = pKa + log [conj. base] •

c) NaNO3 no tiene iones comunes, ni entra en iones ácido -base o complejos

Ksp = [Ca2l-][OH-12. Calculate the reaction quotient using the calculated

Soluciones a los ejercicios

Ka a 1,3 x 10-5 á [H+] [C2H5C00-] _ (x) (0,060 + x) [C2H5COOH] (0.085 - x)

Supongamos que x es pequeño en comparación con 0.060 y 0.085.

x á 4,8 x 10-5 á [OH-], p0H a 4,32, pH a 14,00 - 4,32 a 9,68

(c) mol = M x L; mol CH3COOH = 0.15 M x 0.0500 L = 7.5 x 10 -3 mol

HCOOH(aq)i 0.100 Mc -xe (0.100 - x) M

C5H5N(aq) + H20(1) C5H5NH+ (aq) + OH-( (aq)

(c) mol = M x L; mol HF = 0.050 M x 0.055 L = 2.75 x 10 -3 = 2.8 x 10-3 mol;

not x, as in part (a). buCOOH(aq)equil (a) 0.0075- x equil (b) 0.0075- x M

% ionization = x 100 = 0.018% ionization

Ka = [H+] [CH3CH(OH)C00-] =1.4 x 10-4 [CH3CH(OH)COOH]2+ CH3CH(OH)C00-

(a) Ka =1.4 x 10-4 = X0.125 -x4.2 xX2; x =[H+]= 4.18 x0.12510-3 M H+

(b) Ka =1.4 x 10-4 °°75' x=2.3 x 10-3 M

Buffered Solutions (section 17.2)

a [CH3CH(OH)C001-1] [CH3CF(OH)C00-]1.4 x 10-4 (0.12) [1-1+] = ; 1H+] = 1.53 x

1.4 x 10-4 (0.13 x 0.085)

[}11 =; [H+] = 1.086 x 10-4 = 1.1 x 10-4M; pH = 3.96 (0.15 x0.095)

[H+] = 4.70 x 10-11 = 4.7 x 10-11M; pH = 10.33

[H+] = 6.47 x 10-11 = 6.5 x 10-11M; pH = 10.19

CH3COOH(aq) H+(aq)+ CH3C00-(aq); Ka = 1.8 x 10-5 [H+] [CH3C00-]

[H+] = 5.533 x 10-6 = 5.5 x 10-6 M, pH = 5.26

K = Kw - 1.0 x 10-14 - 5.56 x 10-1° = 5.6 x 10-1°a Kb 1.8 x 10-5

Ka = [H+] [NH3];H [ +]. Ka [NH4+]

5.56 x 10-1° (0.74766 - x) 5.56 x 10-10 (0.74766)(1.00 + x) (1.00)

[WE] = 4.1537 x 10-1° = 4.15 x 10-1° M, pH = 9.382

(a) Ka =6.8 x 10-4 =1.00 - x 1.00

There is 2.6% ionization, so the approximation is valid.

Ka = 6.3x 10-5 = [H+] [C6H5C00]; [C 6 H5 COOH] = 0.0200 M;

[H+] á [C6H5C00-] á xy2

17.27 Analizar/Planificar. Siga la lógica de los ejercicios de ejemplo 17.3 y 17.5.

(a) Ka - [H+] [CH3C00-] ; - Ka [CH3COOH]

1.8 x 10-5 (0.10)

Soluciones a los ejercicios

[H+] tf 1.385 x 10_5 á .4 x1 10-5 M; pH 4,86

(c) CH3C00-(aq) + HN 03 (aq) - CH3COOH(aq) + NO3-(aq)

1,8 x 10-5 (0,12 mol/1,00 L)

[H+] á 1,96 x 10-5 x 2,0 x 10-5 M; pH 4,71

Ka [H+][C2H5C001; [H+] á Ka [C2H5COOH][C2H5COOH][C2H5C00]

volume and work directly with moles.

1.3 x 10-5 (0.15 - x)

1.3 x 10-5 (0.15) .

1.950 x 10-5 = 2.0 x 10-5 M, pH = 4.71

1.6545 x 10-5 = 1.7 x 10-5 M; pH = 4.78

IH(aq) -+ C2H5COOH(aq) + I-(aq)

q) q) [H+] [HCO3-] [HCO3

[HCO3- ] _ 4.3 x 10-7

at pH = 7.1, [H+] = 7.9 x 10- M; .4

6.5 gNaH2PO4 x 1 mol NaH2PO4

8.0 gNa2HPO4 x 1 mol Na2HPO4

There are three CA/CB pairs:

HCOOH/HCOONa, pKa = 3.74

CH3COOH/CH3COONa, pKa = 4.74

H3PO4/NaH2PO4, pKa = 2.12

Since we are making a total of 1 L of buffer,

let y = vol HCOONa and (1 - y) = vol HCOOH.

0.5692 = [HCOONa] _ 0.5692[0.10(1- y)] = 0.10 y;