Tutorial 4 solutions

CM1502
1. Classify each of the following species as a Lewis acid
or a Lewis base:
a. CO
2
b. H
2
O c. I
-
d. SO
2
e. NH
3
f. OH
-
g. H
+
h. BCl
3

(a) Lewis acid;
(b) Lewis base; water combines with H
+
to form H
3
O
+
.
(c) Lewis base.
(d) Lewis acid; SO
2
reacts with water to form H
2
SO
3.
Actually, SO
2
can also act as a Lewis base under some
circumstances.
(e) Lewis base; reaction with H
+
to form ammonium ion.
(f) Lewis base; reaction with H
+
to form water.
(g) Lewis acid;
(h) Lewis acid; compare to the example of NH
3
reacting
with BF
3
.

2. Classify each of these species as a Bronsted acid or
base or both.

a. H
2
O b. OH
-
c. H
3
O
+
d. NH
3
e. NH
4
+
f. NH
2
-
g. NO
3
-

h. CO
3
-
i. HBr j. HCN

(a) both (why?), (b) base,(c) acid, (d) base, (e) acid,
(f) base, (g) base, (h) base,
(i) acid, (j) acid.

3. Calculate the pH of a 0.25 M solution of potassium fluoride
(KF). Calculate the percent of hydrolysis of F
-
base.
Step 1
KF K
+
F
-

Initial 0.25 0 0
Change -0.25 +0.25 +0.25
At eq 0 +0.25 +0.25

Of the ions F- will react with water
F- + H
2
O <=== HF + OH-
Initial 0.25 0 0
Change x +x +x
Eq 0.25-x +x +x

K
b
= 1.4x10
-11
= [HF] [OH
-
] / [F
-
] = x
2
/(0.25-x)

x=1.9x10
-6
=[OH
-
]

pOH = 5.72

pH=8.28


Percent hydrolysis =[F
-
hydrolised]/[F
-
initial]

= 1.9x10
-6
x 100/0.25

= 0.00076%
(a) KF is a weak acid and F
-
is its conjugate base
buffer solution
(b) HBr is a strong acid
not a buffer solution
(c) CO
3
2-
is a weak base and HCO
3
-
is its conjugate acid
buffer solution
4. Which of the following are buffer systems?
(a) KF/HF
(b) KBr/HBr,
(c) Na
2
CO
3
/NaHCO
3


5. Calculate the pH of the 0.30 M NH
3
/0.36 M NH
4
Cl
buffer system. What is the pH after the addition of 20.0 mL
of 0.050 M NaOH to 80.0 mL of the buffer solution?
pKa of NH
4
+
= 9.25
NH
4
+
(aq) H
+
(aq) + NH
3
(aq)
10
[base]
log
[acid]
a
pH pK +
= 9.20
pH = pK
a
+ log
[NH
3
]
[NH
4
+
]
pK
a
= 9.25 pH = 9.25 + log
0.30]
0.36]
= 9.17
NH
4
+
(aq) + OH
-
(aq) H
2
O (l) + NH
3
(aq)
start (moles)
end (moles)
0.029 0.001 0.024
0.028 0.0 0.025
pH = 9.25 + log
[0.25]
[0.28]
[NH
4
+
] =
0.028
0.10
final volume = 80.0 mL + 20.0 mL = 100 mL
[NH
3
] =
0.025
0.10
6. Exactly 100 mL of 0.10 M HNO
2
are titrated with a
0.10 M NaOH solution. What is the pH at the
equivalence point ?
K
b
of NO
2
-
base is 2.2 x 10
-11 ;
pKb of No
2
-
is

10.66

HNO
2
(aq) + OH
-
(aq) NO
2
-
(aq) + H
2
O (l)
start (moles)
end (moles)
0.01 0.01
0.0 0.0 0.01
NO
2
-
(aq) + H
2
O (l) OH
-
(aq) + HNO
2
(aq)
Initial (M)
Change (M)
Equilibrium (M)
0.05 0.00
-x +x
0.05 - x
0.00
+x
x x
[NO
2
-
] =
0.01
0.200
= 0.05 M Final volume = 200 mL
K
b
=
[OH
-
][HNO
2
]
[NO
2
-
]
=
x
2

0.05-x
= 2.2 x 10
-11

0.05 x 0.05 x 1.05 x 10
-6
= [OH
-
]
pOH = 5.98
pH = 14 pOH = 8.02
HA (aq) H
+
(aq) + A
-
(aq)
Initial (M)
Change (M)
Equilibrium (M)
0.122 0.00
-x +x
0.122 - x
0.00
+x
x x
K
a
=
x
2

0.122 - x
= 5.7 x 10
-4

K
a

x
2

0.122
= 5.7 x 10
-4

0.122 x 0.122 K
a
<< 1
x
2
= 6.95 x 10
-5
x = 0.0083 M
0.0083 M
0.122 M
x 100% = 6.8%
More than 5%
Approximation not ok.
7. What is the pH of a 0.122

M monoprotic acid whose
K
a
is 5.7 x 10
-4
?
K
a
=
x
2

0.122 - x
= 5.7 x 10
-4
x
2
+ 0.00057x 6.95 x 10
-5
= 0
ax
2
+ bx + c =0
-b b
2
4ac
2a
x =
x = 0.0081 x = - 0.0081
HA (aq) H
+
(aq) + A
-
(aq)
Initial (M)
Change (M)
Equilibrium (M)
0.122 0.00
-x +x
0.122 - x
0.00
+x
x x
[H
+
] = x = 0.0081 M pH = -log[H
+
] = 2.09
8) Quantitative analysis of Cl
-
ion is often performed by a titration
with silver nitrate, using sodium chromate as an indicator. As
standardized AgNO
3
is added, both white AgCl and red
Ag
2
CrO
4
precipitate where the drop of AgNO
3
lands, but so long
as some Cl
-
remains, the Ag
2
CrO
4
redissolves as the mixture is
stirred. When the red color is permanent, the equivalence point
has been reached.
(a) Calculate the equilibrium constant for the reaction, using the
given data:
2AgCl (s) + CrO
4
2-
(aq) Ag
2
CrO
4
(s) + 2Cl
-
(aq)
AgCl (s) Ag
+
(aq) + Cl

(aq)

K
sp
= 1.8 x 10
-10


Ag
2
CrO
4
(s)

2Ag
+
(aq) + CrO
4
2
(aq)

K
sp
= 2.6 x 10
-12




2AgCl
(s)


2Ag
+
(aq)
+
2Cl
(aq)

K =

(K
sp
)
2
= 3.24 x 10
-20

2Ag
+
(aq)

+

CrO
4
2
(aq)


Ag
2
CrO
4
(s)

K = 1/K
sp
= 3.85 x 10
11

2AgCl(s) + CrO
4
2
(aq)


Ag
2
CrO
4
(s)

+

2Cl

(aq)
K = 1.2 x 10
-8
(b) How many moles per L of AgNO
3
must be added to
0.142 M Na
2
CrO
4
before a red precipitate will occur?

Ag
2
CrO
4
(s)



2Ag
+
(aq)

+ CrO
4
2
(aq) Ksp = 2.6 x 10
-12

Ag
+

2
CrO
4
2
= K
sp
= 2.6 x 10
-12
= (2s)
2
CrO
4
2


2.6 x 10
-12
= (2s)
2
(0.142)

2s = Ag
+
= 4.28 x 10
-6
M

4.28 x 10
-6
mol/L of AgNO
3
has to be added for a red
precipitate to occur.

9) Barium chromate (BaCrO
4
) is a sparingly soluble
salt which has a solubility product K
sp
= 1.1710
-10
at
25 C in water. If it was dissolved in 0.005 molL
-1

Ba(NO
3
)
2
, what is the % difference in the amount that
can dissolve in, as compared to water?
BaCrO
4
(s) Ba
2+
(aq) + CrO
4
2-
(aq)
K
sp
= [Ba
2+
][CrO
4
2-
] = x
2
= 1.1710
-10


x = 1.08 10
-5
molL
-1

In 0.005 molL
-1
Ba(NO
3
)
2
(completely soluble), [Ba
2+
]
= 0.005 molL
-1

So K
sp
= (0.005 + x)(x)

= 1.1710
-10

x
2
+ 0.005x 1.1710
-10
= 0
x = 2.34 x 10
-8


Less 99.8%

10) Amino acids [general formula NH
2
CH(R)COOH] can be
considered polyprotic acids. In many cases, the R group contains
additional amine and carboxyl groups.

Can an amino acid dissolved in pure water have a protonated COOH
group and an unprotonated NH
2
group (K
a
of COOH group = 4.47
10
-3
; K
b
of NH
2
group = 6.03 10
-5
)? Use glycine NH
2
CH
2
COOH,
to explain why.
No. pK
a
of COOH = 2.35 and pK
a
of NH
2
= 9.78 at pH = 7.

pH > pK
a
, base (depronated) form favoured i.e. COO
-
favoured.

pH < pK
a
, acid (pronated) form favoured i.e. NH
3
+
favoured.

b.Calculate [
+
NH
3
CH
2
COO
-
]/[
+
NH
3
CH
2
COOH] at pH 5.5.

Buffer equation:
pH = pK
a
+ log[
+
NH
3
CH
2
COO
-
]/[
+
NH
3
CH
2
COOH]

5.5 = -log(4.47 x 10
-3
) + log[
+
NH
3
CH
2
COO
-
]/[
+
NH
3
CH
2
COOH]

5.5 = 2.35 + log[
+
NH
3
CH
2
COO
-
]/[
+
NH
3
CH
2
COOH]

[
+
NH
3
CH
2
COO
-
]/[
+
NH
3
CH
2
COOH] = 1413

When pH > pKa, base (deprotonated) form is favoured.

11) Calculate [C
4
H
4
O
6
2-
] of a 0.43 molL
-1
solution of
H
2
C
4
H
4
O
6
, given that K
a1
= 1.0 x 10
-3
and K
a2
= 4.6 x 10
-5
.

12) A chemist would like to prepare pH 4.6 acetate buffer. If
he begins with 20 mL of 0.5 molL
-1
acetic acid
(K
a
= 1.8 x 10
-5
), calculate the volume of 0.1 molL
-1

sodium acetate that needs to be added.

22
4.6 = 4.74 + log n
X-
/ n
HX

n
Ac-
/ n
HAc
= 0.724

[n
Ac-
+ (6.0 10
-5
)] / (9.94x10
-3
)

= 0.724

n
Ac-
= 7.14 10
-3
mol

HAc (aq) + H
2
O (l) Ac
-
(aq) + H
3
O
+
(aq)
Equilibrium 0.497 M - 3.0 10
-3 M
3.0 10
-3
M



V
Ac-
= 7.14 10
-3
/ 0.1
= 0.0714 L
= 71.4 mL
9.94x10
-3
mols
6.00 x 10
-5
mols