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( )

O H g . HClO g . solution g .
HClO g . solution g .
solution g
HClO g
.
2 4
4
1 11 5 26 6 37
5 26 6 37
4
705 0
=
=
|
|
.
|

\
|
) ( x
sample total or solution total of mass
ce tan subs of mass
percent Weight % wt 100 = =
( )
L . . / . V
V
L
mol
. L .
L
mol
.
d
d
2 3 25 0 80 0
25 0 00 1 80 0
= =
|
.
|

\
|
= |
.
|

\
|
Chapter 1

1-19 How many grams of perchloric acid, HClO
4
, are contained in 37.6 g of 70.5 wt% aqueous
perchloric acid? How many grams of water are in the same solution?















1-30 What is the maximum volume of 0.25M sodium hypochlorite solution (NaOCl, laundry
bleach) that can be prepared by dilution of 1.00 L of 0.80 M NaOCl?

M
c
V
c
= M
d
V
d


























)
d
(
)
ml / g .
( ' m
m
g/ml 0.0012
g/ml 0.0012

=
1
0 8
1
Chapter 2

2-9 The densities (g/ml) of several substances are:
acetic acid 1.05 CCl
4
1.59 Sulfur 2.07
lithium 0.53 mercury 13.5 PbO
2
9.4
lead 11.4 iridium 22.5
From figure 2.5, predict which substance will have the smallest percentage buoyancy correction
and which will have the greatest.

PbO
2
: lowest correct density closest to 8.0 g/ml
Lithium: largest, lowest density (0.53 g/ml)






































( ) ( )
2 2
01 0 05 0 0510 0 . . . + =
( ) ( )
2 2
95 0 64 1 90 1 . . . + =
Chapter 3

3-16 Find the absolute and percent relative uncertainty and express each answer with a
reasonable number of significant figures:
(c) [4.97 0.05 1.86 0.01]/21.1 0.2 =

Error for subtraction:

= [3.11 0.0510]/21.1 0.2 both 4.97 & 1.86 have two numbers to the right
of decimal point

Error for division, convert to relative uncertainty:

= [3.11 1.64%]/21.1 0.95% 1.64% = 0.051/3.11 & 0.95% = 0.2/21.1




= 0.147 1.90% both 3.11 and 21.1 have 3 significant figures

=0.147 0.003 [1.90% x 0.147 = 0.0027 round up to 0.003]




























( )
% .
.
.
KCl %
g .
KCl mol
KCl g .
AgCl mol
KCl mol
AgCl g .
AgCl mol
AgCl g . gKCl
346 8 100
1367 5
4287 0
4287 0
55 74
1
1
4 143
1
8246 0
= |
.
|

\
|
=
=
|
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
=
010 44
999 21
053 44
2
159 84
6
.
.
.
yl
l .
xl
= |
.
|

\
|
+ |
.
|

\
|
Chapter 27

What is the %KCl in a solid if 5.1367 g of solid gives rise to 0.8246 g AgCl?

Cl
-
+ Ag
+
AgCl(s)








Note: 4 significant figures



27-35 A mixture weighing 7.290 mg contained only cyclohexane, C
6
H
12
(FM 84.159), and
oxirane, C
2
H
4
O (FM 44.053). When the mixture was analyzed by combustion analysis, 21.999
mg of CO
2
(FM 44.010) was produced. Find the weight percent of oxirane in the mixture.

C
6
H
12
+ C
2
H
4
O CO
2
+ H
2
O
FM 84.159 44,053 44.010


Let x = mg of C
6
H
12
and y = mg of C
2
H
4
O

x + y = 7.290

Also: CO
2
= 6 (moles of C
6
H
12
) + 2(moles of C
2
H
4
O)

Conserve number of carbon atoms:






Make substitution x = 7.290 y and solve for y

y = 0.767 mg = 0.767 mg / 7.290 mg = 10.5 wt%







27-21. A mixture containing only Al
2
O
3
(FM 101.96) and Fe
2
O
3
(FM 159.69) weighs 2.019 g.
When heated under a stream of H
2
, Al
2
O
3
is unchanged, but Fe
2
O
3
is converted into metallic Fe
plus H
2
O (g). If the residue weighs 1.774 g, what is the weight percent of Fe
2
O
3
in the original
mixture?

heat
Fe
2
O
3
+ Al
2
O
3
Fe + Al
2
O
3

H
2


2.019 g 1.774 g


Mass of oxygen lost: 2.019 g 1.774 g = 0.245 g

Moles of oxygen atoms lost: (0.245 g )(1 mole / 15.9994 g) = 0.01531 moles

Fe
2
O
3
: 3 moles of oxygen = 1 mole of Fe
2
O
3


Moles of Fe
2
O
3
= 1/3(0.01531) = 0.005105

Mass of Fe
2
O
3
= (0.005105 moles)(159.69 g /mole) = 0.815 g

wt% = (0.815 g / 2.019 g)x100 = 40.4%


























6 108
5
3 108 8 106 2 114 9 97 0 116
.
. . . . .
) x ( Mean =
+ + + +
=
( ) ( ) ( ) ( )
( )
1 7 985 50
4
94 203
4
09 0 24 3 36 31 49 114 76 54
4
09 0 24 3 36 31 49 114 76 54
1 5
6 108 3 108 6 108 8 106 6 108 2 114 6 108 9 97 6 108 0 116
2 2 2 2 2
. . ) s ( Deviation dard tan S
. . . . . . . . . . .
) s ( Deviation dard tan S
) . . ( . . . . . . . .
) s ( Deviation dard tan S
= =
=
+ + + +
=
+ + + +
=

+ + + +
=
00 4
1 7
2 80 6 108
.
.
. .
s
x x
z =

~
( )( )
( )
8 6 6 108
5
1 7 132 2
6 108 . .
. .
.
n
ts
x = = =
Chapter 4

4-A(i) For the following bowling scores 116.0, 97.9, 114.2, 106.8 and 108.3, find the mean,
median, range and standard deviation.




Median = 97.9, 106.8, 108.3, 114.2, 116.0 108.3 (middle)

Range = 116.0 97.9 = 18.1











4-A(ii) A bowler has a mean score of 108.6 and a standard deviation of 7.1. What fraction of the
bowlers scores will be less than 90.2?


Determine how many standard deviations the value 80.2 is from the mean.



From Gaussian table:

Area below 2.60 standard deviation is 0.5000 - 0.499968 = 0.000032 = 3.2x10
-3
%
Therefore, the bowler only has a 3.2x10
-3
% chance of bowling a game below 80.2


4-A(iii) For the following bowling scores 116.0, 97.9, 114.2, 106.8 and 108.3, a bowler has a
mean score of 108.6 and a standard deviation of 7.1. What is the 90% confidence interval for the
mean?


Degrees of freedom 5-1 =4, 90% confidence from students t table = 2.132
95% confident range contains true mean : (true mean between 12.0 & 13.0)


64 0 49 0
1 18
9 8
9 97 0 116
9 97 8 106
. Q .
.
.
. .
. .
Range
Gap
Q
table
= < = =

= =
4-A(iv) For the following bowling scores 116.0, 97.9, 114.2, 106.8 and 108.3, a bowler has a
mean score of 108.6 and a standard deviation of 7.1. Using the Q test, decide whether the
number 97.9 should be discarded.

97.9, 106.8, 108.3, 114.2, 116.0





Therefore, 97.9 should be retained.






































g .
.
. .
m
b y
x
1
0
0
7 8
0163 0
104 0 246 0
=

=
) . ( .
) . ( . ) . ( .
m
b y
x
2 0
6 0 9
0002 0 0163 0
002 0 104 0 005 0 246 0

=
%) . or ( g . g . x
7 1
4 4 0 7 8 =
counts . ) . ( y
dl
6 129 2 28 3 45 = + =
M
counts
x .
M . ion concentrat sample
y e y
m
blank sampl
9
10 752 1
00 1
45 1797
=

M x .
M / counts x .
) . )( (
m
s
c
8
9
10 8 4
10 752 1
2 28 3 3

= = =
Chapter 5

Ex: The amount of protein in a sample is measured by the samples absorbance of light at a given
wavelength. Using standards, a best fit line of absorbance vs. mg protein gave the following
parameters:
m = 0.0163
0
s
m
= 0.0002
2


b = 0.104
0
s
b
= 0.002
6

An unknown sample has an absorbance of 0.246 0.005
9.
What is the amount of protein in the
sample?











5-19. Low concentrations of Ni-EDTA near the detection limit gave the following counts in a
mass spectral measurement: 175, 104, 164, 193, 131, 189, 155, 133, 151, 176. Ten measurements
of a blank had a mean of 45 counts. A sample containing 1.00 mM Ni-EDTA gave 1,797 counts.
Estimate the detection limit for Ni-EDTA

Standard deviation for the 10 measurements: 28.2

Detection limit:

Convert counts to molarity:



Minimum detectable concentration:













5-24 Tooth enamel consists mainly of the mineral calcium hydroxyapatite, Ca
10
(PO
4
)
6
(OH)
2
.
Trace elements in teeth of archaeological specimens provide anthropologists with clues about
diet and disease of ancient people. Students at Hamline University measured strontium in enamel
from extracted wisdom teeth by atomic absorption spectroscopy. Solutions with a constant total
volume of 10.0 mL contained 0.750 mg of dissolved tooth enamel plus variable concentrations of
added Sr.

Find the concentration of Sr.

Added Sr (ng/mL = ppb) Signal (arbitrary units)
0 28.0
2.50 34.3
5.00 42.8
7.50 51.5
10.00 58.6



y = 3.136x + 27.36

y-intercept = -8.72 ng/mL = ppb concentration of unknown in the 10 mL sample



















1684 0
72 1
10222
47 3
3473
. F
.
F
. ] S [
As
F
] X [
Ax
= |
.
|

\
|
= = =
847 0
00 10
00 1
47 8 .
mL .
mL .
) . ( ] S [ = |
.
|

\
|
=
M . ] X [
.
.
] X [ ] S [
As
F
] X [
Ax
16 6
847 0
4431
1684 0
5428
= |
.
|

\
|
= = =
M .
mL .
mL .
) . ( ] x [ 3 12
00 5
00 10
16 6 = |
.
|

\
|
=

5.29 A solution containing 3.47 mM X (analyte) and 1.72 mM S (standard) gave peak areas of
3,473 and 10,222, respectively, in a chromatographic analysis. Then 1.00 mL of 8.47 mM S was
added to 5.00 mL of unknown X, and the mixture was diluted to 10.0 mL. The solution gave
peak areas of 5,428 and 4,431 for X and S, respectively
(a) Calculate the response factor for the analyte
(b) Find the concentration of S (mM) in the 10.0 mL of mixed solution.
(c) Find the concentration of X (mM) in the 10.0 mL of mixed solution.
(d) Find the concnetration of X in the original unknown.

(a)



(b) Simple dilution






(c) Use answers to a and b





(d) Simple dilution





















69
10 3 2

= . K
sp
69 6 6 4
10 3 2
4
1
10 0 1
+
= = = x . ) x ( ) x . ( ) x ( ] [SO ] [OH ] [Cu K
- 2
4
6 - 4
sp
M x . x x . x x . ) x . ( ) x (
7 33 5 69 37 5
10 9 3 10 2 9 10 3 2 10 5 2

= = = =
69 6 6 4
10 3 2 10 0 10 0 1
+
= = = x . ) . ( ) x . ( ) x ( ] [SO ] [OH ] [Cu K
- 2
4
6 - 4
sp
M x . x x . x x . ) x . ( ) x (
8 32 4 69 37 4
10 2 1 10 3 2 10 3 2 10 0 1

= = = =
Chapter 6

6-16: Find [Cu
2+
] in a solution saturated with Cu
4
(OH)
6
(SO
4
) if [OH
-
] is fixed at 1.0x10
-6
M.
Note that Cu
4
(OH)
6
(SO
4
) gives 1 mol of SO
4
2-
for 4 mol of Cu
2+
?



[K
sp
table appendix F on page AP9]

Let x = [Cu
2+
], then [SO
4
2-
]=1/4x








6-16 (B). Find [Cu
2+
] in a solution saturated with Cu
4
(OH)
6
(SO
4
) if [OH
-
] is fixed at 1.0x10
-6
M
and 0.10M Na
2
SO
4
is added to the solution.



Cu
4
(OH)
6
(SO4) Cu
+
OH
-
SO
4
-2

Initial
Concentration
solid 0 1.0x10
-6
0.10M
Final
concentration
solid x 1.0x10
-6
1/4x + 0.10M


Let x = [Cu
2+
], then [SO
4
2-
]=1/4x
Assume 1/4x << 0.10M





Check assumption: ( )1.2x10
-8
<< 0.10M
3.1x10
-9
<< 0.10M true


1.2x10
-8
M < 3.9x10
-7
M solubility of Cu
2+
is reduced




( )( )( ) M . . . .
.
5 7 3 4
2
1
4
2
1
10 3 2 10 2 3 10 9 2 10 5 2
10 5 2

+ +
+
+
= =
= = = ] ][ [ ] (OH) [
] ][ [
] (OH) [ -
-
OH Zn Zn
OH Zn
Zn
| |
M .
) x . (
.
K
. K
sp
sp
3
2 7
16
16
10 9 2
10 2 3
10 0 3
10 0 3

+ +
=

= = = =
2 -
2 2 2
] [OH
] [ ] ][ [ Zn OH Zn
-
( )( )( ) M . . . .
.
7
3
7 3 15
2
3
15
2
3
10 8 6 10 2 3 10 9 2 10 2 7
10 2 7

+
+

= =
= = =
3 -
3
3 -
3
] ][ [ ] (OH) [
] ][ [
] (OH) [
OH Zn Zn
OH Zn
Zn
| |
( )( )( ) M . . . .
.
14
4
7 3 15
2
4
15
2
4
10 5 8 10 2 3 10 9 2 10 8 2
10 8 2

+
+

= =
= = =
4 -
4 -
] ][ [ ] [
] ][ [
] [
OH Zn Zn(OH)
OH Zn
Zn(OH) 2
4
2
4
| |
0 6 10 1
6
. ) M log( ] H log[ pH = = =
+
M .
) x . (
.
K
. K
sp
sp
3
2 7
16
16
10 9 2
10 2 3
10 0 3
10 0 3

+ +
=

= = = =
2 -
2 2 2
] [OH
] [ ] ][ [ Zn OH Zn
-
6-25 Given the following equilibria, calculate the concentration of each zinc-containing species in
a solution saturated with Zn(OH)
2
(s) and containing [OH
-
] at a fixed concentration of 3.2x10
-
7
M.

Zn(OH)
2
(s) K
sp
= 3.0x10
-16

Zn(OH
+
) |
1
= 2.5 x10
4

Zn(OH)
3
-
|
3
= 7.2x10
15

Zn(OH)
4
2-
|
4
= 2.8x10
15






















pH Ex: (a) What is the pH of a solution containing 1x10
-6
M H
+
?





(b) What is the [OH
-
] of a solution containing 1x10
-6
M H
+
?







5
10
14
10 6 1
10 2 6
10 0 1

=
= =
.
) . (
) . (
K
K / K K K K K
b
a w b b a w
6-49. Write the K
b
reaction of CN
-
. Given that the K
a
value for HCN is 6.2x10
-10
, calculate K
b
for
CN
-
.


CN
-
+ H
2
O <--> HCN + OH
-












































Chapter 7

7-A (a) Suppose 29.41 mL of I
3
-
solution is required to react with 0.1970 g of pure ascorbic acid,
what is the molarity of the I
3
-
solution?

(0.1970g)(1 mole/176.124 g) = 1.1185x10
-3
mol (1.1185 mmol) of ascorbic acid

1 mole ascorbic acid = 1 mole I
3
-
1.1185 mmol I
3
-

Molarity of I
3
-
: 1.1185 mmol/29.41 mL = 0.03803 M

(b) A vitamin C tablet containing ascorbic acid plus an inert binder was ground to a powder, and
0.4242g was titrated by 31.63 mL of I
3
-
. Find the weight percent of ascorbic acid in the
tablet.

(31.63 mL)(0.03803M) = 1.203 mmol of I
3
-

1 mole ascorbic acid = 1 mole I
3
-
1.203 mmol ascorbic acid

(1.203x10
-3
mol)(176.124 g/mol) = 0.2119g ascorbic acid

(0.2119g)/(0.4242g)x100 =49.94%
















=
i
i i
z c
2
2
1

07 2 10 6 8 86 0 010 0
3
. ] . log[ )] . )( . log[( ] H log[ A log pH
H H
= = = = =
+
+ +

00 2 010 0 . ] . log[ ] H log[ A log pH
H H
= = = =
+ +
+

Chapter 8

8-3. What is the ionic strength of a 0.0087 M KOH and 0.0002 M La(IO
3
)
3
solution? Assume
complete dissociation and no formation of LaOH
2+





[K
+
]=[OH
-
]=0.0087
3x[La
+3
] =[IO
3
-
]

K
+
OH
-
La
+3
IO
3
-

[0.0087x1
2
+0.0087x(-1)
2
+ 0.0002x3
2
+0.0006x(-1)
2
] = 0.0099 M




8-11. What is the pH of a solution containing 0.010M HCl plus 0.040 M KClO
4
?


First determine the ionic strength of the solution, since the ion charges are all 1:

= 0.010M (HCl) + 0.040M (KClO
4
) = 0.050 M

Using table,
H+
= 0.86

[H
+
] = 0.010M




Ignoring difference between activity and concentration:
















M .
.
.
x
x . x ) . )( . )( ( x . K
) x ( ) x ( B Hg A A K
Br
Hg
sp
Br
Hg
Br
Hg
Br
Hg
sp
8
3
23
3 3 2 2 3 23
2 2 2 2 2
2
2
10 6 2
223 3
10 6 5
223 3 964 0 867 0 4 4 10 6 5
2
2
2
2
2
2
2
2
2

+
=

=
= = = =
= = =

+

] r [ ] [
M x . Hg
) . ( ) M . )( . (
x .
B
K
Hg
B Hg A A K
Br
Hg
sp
Br
Hg
Br
Hg
sp
17 2
2
2 2
23
2 2
2
2
2 2 2
2
2
10 0 7
964 0 00100 0 867 0
10 6 5
2
2
2
2
2
2
+

+
+
=
= =
= =

+
] [
] r [
] [
] r [ ] [


8-9 (a) What is the [Hg
2
2+
] in a saturated solution of Hg
2
Br
2
with 0.00100M KCl, where
and KCl acts as an inert salt?



First determine the ionic strength, = 0.00100M (KCl) negligible contribution from
Hg
2
Br
2


Using table,
Hg2+
= 0.867,
Br-
= 0.965

[Hg
2
+2
] = x, [Br
-
] = 2x











(b) What is the [Hg
2
2+
] in a saturated solution of Hg
2
Br
2
with 0.00100M KBr?




First determine the ionic strength, m = 0.00100M (KBr) negligible contribution from
Hg
2
Br
2


Using table, g
Hg2+
= 0.867, g
Br-
= 0.965

[Br
-
] = 0.00100M (KBr), negligible contribution from Hg
2
Br
2















8-24 Write a mass balance for a solution of Fe
2
(SO
4
)
3
, if the species are Fe
3+
, Fe(OH)
2+
,
Fe(OH)
2
+
, Fe
2
(OH)
2
4+
, FeSO
4
+
, SO
4
2-
and HSO
4
-
.

Fe
2
(SO
4
)
3
3(total Fe) = 2(total SO
4
)

(3){[Fe
3+
] + [Fe(OH)
2+
] + [Fe(OH)
2
+
] + 2[Fe
2
(OH)
2
4+
] +[ FeSO
4
+
] } =

(2){[ FeSO
4
+
] + [SO
4
2-
] + [HSO
4
-
]}

2 in front of Fe
2
(OH)
2
4+
because it contains 2 Fe.



20 4 10 35 6
10 35 6
10 0450 0
10
5
5
78 2
2 78 2
. ] x . log[ pKa
.
) . (
) (
] HA [
] A ][ H [
K
.
.
a
= =
=

= =

+
% . .
.
x .
M .
M
F
x
.
69 3 0369 0
0450 0
10 66 1
0450 0
10
3 78 2
= = = = =

o
mL .
M .
mol .
volume
mol .
.
x .
x x . x .
x .
x
.
x .
x
log .
x .
x
log . .
log pK . pH
a
2 16
626 0
01017 0
01017 0
832 1
10 86 1
832 1 10 86 1
0224 0
832 0
0224 0
08 0
0224 0
48 7 40 7
40 7
2
2
= =
= = =

=

+ =
|
|
.
|

\
|
+ = =

] [
] [
HA
A
-
Chapter 9

9-11. (a) A 0.0450 M solution of benzoic acid has a pH of 2.78. Calculate pK
a
for this acid







Concentrations: HA A
-
H
+

F-10
-2.78
10
-2.78
10
-2.78


F=0.0450M; pH =-log[H
+
]; [H
+
] = 10
-pH
= [A
-
]









(b) What is the percent fraction dissociation?





9-40. (a) Calculate how many milliters of 0.626 M KOH should be added to 5.00 g of MOBS
(FW: 223.29) to give a pH of 7.40?


HA OH
-
A
-

Initial moles: 0.0224 x -
Final moles: 0.0224-x - x




64 7 453 1 48 7
01327 0 0224 0
01327 0
48 7
40 7
. ) . log( .
. .
.
log . pH
log pK . pH
a
= + =

+ =
|
|
.
|

\
|
+ = =
] [
] [
HA
A
-
(b) What is the pH if an additional 5 mL of the KOH solution is added?


Total moles of KOH = (21.2 ml)(0.626M)=0.01327 mol








g . x
. / x .
.
x
log .
) mol / g . /( ) g . (
) mol / g . /( ) xg (
log . . log pK pH
a
96 2
3089 6 4688 0
3089 6
329 0
0 84 00 5
99 105
329 10 00 10
2
=
=
=
+ = =
|
|
.
|

\
|
+ =
] [
] [
-
3
- 2
3
HCO
CO
972 2
1
. pK
a
=
7 13
2
. pK
a
=
mmol . x
x . .
x x . .
x . / x .
x .
x
log .
x .
x
log . .
4493 0
373 4 965 1
373 3 965 1
5825 0 373 3
5825 0
528 0
5825 0
972 2 50 3
=
=
=
=

=

+ =
NaOH mL . ) M . /( ) mmol . ( 223 2 202 0 4493 0 =
Chapter 10

10-11 How many grams of Na
2
CO
3
(FM 105.99) should be mixed with 5.00 g of NaHCO
3
(FM
84.01) to produce 100 mL of buffer with pH 10.00?

We know, [CO
3
-2
] and [HCO
3
-
], so use pK
a2

pK
a
from Appendix G acid dissociation constants page AP12









Note: volume not used since it simply cancels.


10-12 How many milliliters of 0.202 M NaOH should be added to 25.0 mL of 0.0233 M of
salicylic acid (2-hydroxybenzoic acid) to adjust the pH to 3.50?
Treat as monoprotic acid
At pH 3, mixture of H
2
A and HA
-
Moles of salicylic acid (H
2
A) = (25.0 mL)(0.0233 M) = 0.5825 mmol

H
2
A OH
-
HA
-

Initial moles: 0.5825 x -
Final moles: 0.5825-x - x






351 6
1
. pK
a
=
329 10
2
. pK
a
=
mL . ) MKOH . / ) mol . ( mol . . . moles KOH Total
mol . x
x . .
x x . .
x . / x .
x .
x
log .
x .
x
log . .
] HHis [
] His [
log pK pH
9 78 00 1 0789 0 0789 0 05219 0 02670 0
02670 0
047 2 0546496 0
047 1 0546496 0
05219 0 047 1
05219 0
02 0
05219 0
28 9 30 9
3
= = + =
=
=
=
=

=

+ = = + =

10-20 How many milliters of 1.00 M KOH should be added to 100 mL of solution containing
10.0 g of histidine hydrochloride (His
.
HCl FM 191.62) to get a pH of 9.30?























Treat as monoprotic acid.
histidine hydrochloride is the intermediate form (H
2
His
+
) between pK
1
& pK
2
.

1) Must add enough KOH (1:1 molar ratio) to convert all H
2
His
+
to HHis
2) Must added more KOH to obtain mixture of HHis and His
-
to obtain pH of 9.30


Initial moles of H
2
His
+
= 10.0g/(191.62 g/mol) = 0.05219 mol

Require 0.05219 mol of KOH plus:

HHis OH
-
His
-

Initial moles: 0.05219 x -
Final moles: 0.05219-x - x









18 8 10 50 1 10 50 1
10 25 2 10 757 6 0
10 757 6
10 48 1
10 0 1
0333 0
6 6
12 11 2
11
4
14 2 2
. ) x . log( pH M x . x quadratic solve
x . x x . x
x .
x .
x .
K
K
K
x .
x
K
K
K
x F
x
a
w
b
a
w
b
= = =
+ =
= = = =

= = =

Chaper 11


11-8 a) What is the pH at the equivalence point when 0.100 M hydroxyacetic acid is titrated with
0.0500 M KOH?



Equivalence point exactly enough KOH to consume hydroxyacetic acid (HA)

Twice the volume of KOH (0.0500) is required to titrate hydroxyacetic acid (0.100)

Formal concentration of A
-
= (volume of HA/(volume of HA + volume KOH))(0.100M)
= V/(V+2V)(0.100M) set V = 1
= 1/(1+3)(0.100M)
= 0.0333M

The solution only contains A
-
weak base (K
a
= 1.48x10
-4
, Appendix G, AP14)




F-x x x











b) What indicator would be a good choice to monitor the endpoint?

Cresol red to phenolphtelen or any number of inidcators that change color around
pH 8.18 (see table)











22
3
10 46 5
10 0
=

= =
+
.
) x )( x (
) x . (
] EDTA ][ Fe [
] ) EDTA ( Fe [
K
-
'
f
12 3
10 4 1
+
= = = . ] EDTA [ ] Fe [ x
Chapter 12

ex: What is the concentration of free Fe
3+
in a solution of 0.10 M Fe(EDTA)
-
at pH 8.00?

K
f
= 10
25.1
=1.3x10
25
from table 12-2

Y4-
at pH 8.0 = 4.2x10
-3
from table 12-1












Solve quadratic for x:





Fe
3+
EDTA Fe(EDTA)
-

Initial conc: 0 0 0.10
Final conc: x x 0.10-x
V . . . E E E
cell
69 0 229 1 92 1 = = =
+
J x . )
C
J
. )(
mol
C
x . )( mol ( nFE G
5 4
10 7 2 69 0 10 649 9 4 = = = A
2812 0 0592 0 222 0
10 0
2
05916 0
222 0
2
05916 0
222 0
2 2
. . . E
] M . log[
.
. ] Cl log[
.
. E : cell half right
= + =
= =
+

+
908 2 0592 0 350 0
10 0
2
05916 0
222 0
2
05916 0
350 0
2 2
. . . E
] M . log[
.
. ] F log[
.
. E : cell half left
= + =
= =

V . ) . ( . E E E
cell
572 0 908 2 2812 0 = = =
+
Chapter 14


14-25 (a): Calculate E
o
and AG
o
for the following reaction:




Identify the half-reactions, look for atoms that with a change charge (ionic) state:
Standard reaction potentials are listed in appendix H.

E
+
o
= 1.92V
-
E
-
o
= 1.229V
E
o
= 0.69V








14-19 (a) : Calculate the cell voltage if the concentration of NaF and KCl were each 0.10 M in
the following cell:
(anode, E
-
) Pb(s) | PbF2(s) | F
-
(aq) || Cl
-
(aq) | AgCl(s) | Ag(s) (cathode, E
+
)

Identify the half-reactions, look for atoms that with a change charge (ionic) state:
Standard reaction potentials are listed in appendix H.

E
o
= 0.222

E
o
= -0.350


Solve the Nernst equation for each half-reaction:



V . . . E E E
cell
339 0 356 0 017 0 = = =
+
6
05916 0
339 0 1
05916 0
10 9 1 10 10

= = = = x . K K
.
) . )( (
.
nE
sp
o
5
2
2
2
2
2
2
2 2
2
10 85 1
10 348 1
0025 0
0025 0
10 348 1
0025 0
1298 2
0025 0
2
05916 0
575 0 512 0
0025 0
2
05916 0
575 0
2
05916 0
512 0
+
+
+
+
+ +
+
= =
=
=
=

= = =
x .
x .
] M . [
] Cu [
] Cu [
] M . [
x .
] Cu [
] M . [
log .
] Cu [
] M . [
log
.
) V . V . (
] Cu [
] M . [
log
.
.
] Cu [
] Ni [
log
.
E V . E
o
7 2 5 2
3
2
10 85 1 10 0 10 85 1
+
= = = x . ) . )( x . ( ] I O ][ Cu [ K
sp
14-25 (b): Calculate K for the following reaction:




Identify the half-reactions, look for atoms that with a change charge (ionic) state:
Standard reaction potentials are listed in appendix H.

E
+
o
= 0.017V
-
E
-
o
= 0.356V
E
o
= -0.339V









14-40: If the voltage for the following cell is 0.512V, find K
sp
for Cu(IO
3
)
2
:



Identify the half-reactions, look for atoms that with a change charge (ionic) state:
Standard reaction potentials are listed in appendix H.

E
+
o
= 0.339V

E
-
o
= -0.236V

E
o
= 0.575V


] Ag [
log
.
. E
+
+
=
1
1
05916 0
799 0
V . l E
.
] M . [
log
.
. E
cel
cell
445 0
241 0
0125 0
1
1
05916 0
799 0
=
=
Chapter 15

15-8: A 10.0 mL solution of 0.0500 M AgNO3 was titrated with 0.0250M NaBr in the cell:

S.C.E. || titration solution | Ag(s)

Find the cell voltage for 10.0 mL of titrant.

The equivelence volume (Ve) = 20.0 mL [20.0 mL x 0.250M = 10.0 mL x 0.0500M]

Titration reaction relative to S.C.E (E
-
= 0.241V):

E
+
o
= 0.799V





[Ag+] = (10.0/20.0)(0.0500M)(10.0/20.0)=0.0125M



Fraction Dilution
Remaining Factor (original volume/final volume)
(original volume-added volume)/total volume








Chapter 16


16-17: A 50.00 mL sample containing La
3+
was titrated with sodium oxalate to precipitate
La
2
(C
2
O
4
)
3
, which was washed, dissolved in acid, and titrated with 18.0 mL of 0.006363
M KMnO
4
. Calculate the molarity of La
3+
in the unknown.

Need to identify the titration reaction, first determine the two reactions.

Oxidation with Potassium permanganate:

Reduction:





Oxidation:





Then write a balanced reaction:


18.04 mL of 0.006363 M KMnO
4
= 0.1148 mmol of MnO
4
-


Reacts with (5/2)(0.1148) = 0.2870 moles of H
2
C
2
O
4


which came from (2/3)(0.2870) = 0.1913 mmol of La
3+
[La
2
(C
2
O
4
)
3
]

[La
3+
] = 0.1913 mmol/50.00 mL = 3.826 mM


Chapter 18

18-B: A 3.96x10-4 M solution of compound A exhibited an absorbance of 0.624 at 238 nm in a
1.000 cm cuvet. A blank had an absorbance of 0.029. The absorbance of an unknown solution
of compound A was 0.375. Find the concentration of A in the unknown.

First, find the molar absorptivity of compound A:

1 1 3
4
10 50 1
000 1 10 96 3
029 0 624 0

= = cm M x .
) cm . )( M x . (
. .
cb
A
c (Correct absorbance for blank)


Use molar absorptivity to calculate concentration of unknown:

M x .
) cm . )( cm M x . (
. .
b
A
c
4
1 1 3
10 31 2
000 1 10 50 1
029 0 375 0


=

= =
c




18-20: In formaldehyde, the transition n p*(T
1
) occurs at 397 nm, and the np*(S
1
) transition
comes at 355 nm. What is the difference in energy (kJ/mol) between the S
1
and T
1
states?


n t*(T
1
)

J x .
m x
s x .
J s x .
c
h h E
19
9
1 8
34
10 00 5
10 397
10 9979 2
10 6261 6

= = = =

v

Convert to J/mol, multiply by Avogadros number

mol / kJ mol / molecules x . molecule / J x . 301 10 022 6 10 00 5
23 19
=




n p*(S
1
)

J x .
m x
s x .
J s x .
c
h h E
19
9
1 8
34
10 60 5
10 355
10 9979 2
10 6261 6

= = = =

v

Convert to J/mol, multiply by Avogadros number

mol / kJ mol / molecules x . molecule / J x . 337 10 022 6 10 60 5
23 19
=



The difference between the T
1
and S
1
statest is 337-301 = 36 kJ/mol


Chapter 23

23-11: Butanoic acid has a partition coefficient of 3.0 (favoring benzene) when distributed
between water and benzene. Find the formal concentration of butanoic acid in each phase
when 100 mL of 0.10 M aqueous butanoic acid is extracted with 25 mL of benzene at pH
4.00 and pH 10.00.

K
a
for butanoic acid = 1.52x10
-5
from appendix G AP12

At pH 4.00:

60 2
10 52 1 10
10 3
5 00 4
00 4
.
) x . (
) )( (
) K ] H ([
] H [ K
D
.
.
a
=
+
=
+
=

+
+



Fraction remaining in water:


606 0
25 60 2 100
100
2 1
1
.
) mL . mL (
mL
) DV V (
V
q =
+
=
+
=


Molarity in water:


M . ) M . )( . ( ] acid oic tan bu [ 0606 0 10 0 606 0 = =

Molarity in benzene:

Total moles in system = mol . ) M . )( L . ( 010 0 10 0 100 0 =

Fraction in benzene = (1-0.606) = 0.394

Molarity in benzene = (0.394)(0.010 mol)/(0.025 L) = 0.16 M


At pH 10.00:

5
5 00 10
00 10
10 97 1
10 52 1 10
10 3

+
+
=
+
=
+
= x .
) x . (
) )( (
) K ] H ([
] H [ K
D
.
.
a







Fraction remaining in water:


9999951 0
25 10 97 1 100
100
5
2 1
1
.
) mL x . mL (
mL
) DV V (
V
q =
+
=
+
=




Molarity in water:

M . ) M . )( (~ ] acid oic tan bu [ 10 0 10 0 1 = =

Molarity in benzene:

Total moles in system =
mol . ) M . )( L . ( 010 0 10 0 100 0 =


Fraction in benzene = (1-0.9999951) = 4.9x10
-4


Molarity in benzene = (4.9x10
-4
)(0.010 mol)/(0.025 L) = 2x10
-6
M






23-24: The retention volume of a solute is 76.2 mL for a column with V
m
= 16.6 mL and V
s
=
12.7 mL. Calculate the capacity factor and the partition coefficient for this solute.


V
m
volume of mobile phase
V
s
volume of stationary phase

Capacity factor:

59 3
6 16
6 16 2 76
.
.
. .
V
V V
V
V
' k
m
m r
m
'
r
=

= =


Partition coefficient:

69 4
7 12
6 16
59 3 .
.
.
) . (
Vs
V
' k K
m
= = =








23-42: Two compounds with partition coefficients of 15 and 18 are to be separated on a column
with V
m
/V
s
= 3.0 and tm = 1.0 min. Calculate the number of theoretical plates needed to
produce a resolution of 1.5


Want Rs = 1.5,
( ) 1
4
5 1 = =
N
. R
s


Need t
2
and t
1


0 6
0 3
1
18
2 2
.
. Vm
V
K ' k
s
= = = 0 5
0 3
1
15
1 1
.
. Vm
V
K ' k
s
= = =

min . ) . min)( . ( ) ' k ( t t
t
t t
' k
m
m
m
0 6 1 0 5 0 1 1
1 1
1
1
= + = + =

=

min . ) . min)( . ( ) ' k ( t t
t
t t
' k
m
m
m
0 7 1 0 6 0 1 1
2 2
2
2
= + = + =

=

Determine

167 1
0 6
0 7
1
2
.
.
.
t
t
= = =


Determine N

( )
plates x . N
.
) )( . (
N
.
N
. R
s
3
10 3 1
36
167 0
4 5 1
1 167 1
4
5 1
=
= =
= =