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CHAPTER 5

A. Calculations Based on Weight Relations of Formulas and Equations


(Use chemical factors whenever possible in solving the problem of this section)
1. Calculate the chemical factors:
Weighed Sought Factor
(NH4)2PtCl6 NH3 0.0766/0.077_
AgCl Mg(ClO4)2 ___ __0.779 _ _ _

Cu2S CuO 1.000

K2PtCl6 K 0.1605/1.61_

Pb3O4 Pb 0.9066/0.97

BaSO4 FeS2 0.2568/0.257

CaO H2C2O4∙2H2O none


Solutions

a. (NH4)2PtCl6 = 2NH3 + 2HCl +2Cl2 + Ptons


(NH4)2PtCl6 2NH3 Factor = Sought
Cl= 35.45 x 6 = 212.7 N= 14 x 2 = 28 Weighed
N= 14 x 2 = 28 H=1x3x2=6 Factor = 2NH3
H= 4 x 2= 8 = 34 (NH4)2PtCl6
Pt =195 Factor = 34
= 443.7 443.7
Factor= 0.0766/0.077
b. MgCl2 + 2AgClO4 = Mg (ClO4)2 + 2AgCl

2AgCl Mg (ClO4)2 Factor = Sought

Cl= 35.45 x 2 = 70.90 Mg = 24.30 Weighed


Ag= 107.86 x 2 = 215.72 Cl= 35.45 x 2 = 70.90 Factor = Mg (ClO4)2
= 296.62 O= 16 x 4 x 2 = 128 2AgCl
= 223.2 Factor = 223.2
296.62
Factor = 0.779

c. 2CuO + Cu2S = 4Cu + SO2


2CuO Cu2S Factor = Sought
Cu = 63.54 x 2 = 127.08 Cu = 63.54 x 2 = 127.08 Weighed
O = 16 x 2 = 32 S = 32.07 Factor = 2CuO
= 159.08 = 159.15 Cu2S
Factor = 158.08
Factor= 0.999/1.000 159.15
d. 2K + Pt + Cl6 = K2PtCl6
K2PtCl6 2K Factor = Sought
K = 39 x 2 = 78 K = 39 x 2 = 78 Weighed
Pt = 195 =78 Factor = 2K
Cl = 35.45 x 6 = 212.7 K2PtCl6
= 485.7 Factor = 78
485.7
Factor= 0.1605/0.161
e. 3Pb + 2O2 = Pb3O4
Pb3O4 3Pb Factor = Sought
Pb= 207.2 x 3 = 621.6 Pb = 207.2 x 3 = 621.6 Weighed
O = 16 x 4 = 64 = 621.6 Factor = 3Pb
= 685.6 Pb3O4
Factor = 621.6
685.6
Factor= 0.9066/0.907
f. 2BaSO4 + FeS2 = Fe (SO4)2 + 2BaS
2BaSO4 FeS2 Factor = Sought
Ba= 137.32 x 2 = 274.64 Fe = 55.85 Weighed
S = 32 x 2 = 64 S = 32 x 2 = 64 Factor = FeS2
O = 16 x 4 = 64 x 2 = 128 = 119.85 2BaSO4
= 466.64 Factor = 119.85
466.64
Factor= 0.2568/0.257

2. Calculate by factors the following:


a. The tons of limestone (CaCo3) needed for the preparation of 5 tons of lime (CaO).

𝐶𝑎𝐶𝑂3 = 100.09
CaO = 56.08
3
Weight of 𝐶𝑎𝐶𝑂3 = 5 tons of CaO × 𝐶𝑎𝐶𝑂
𝐶𝑎𝑂

= 5 tons of CaO × 100.09


56.08
= 8.9 / 9 tons

b. The pounds of BaCl2 needed to furnish 1.50 lb of chlorine by an electrolytic process.

𝐵𝑎𝐶𝑙2 = 208.23
Cl = 35.45
𝐵𝑎𝐶𝑙2
Weight of 𝐵𝑎𝐶𝑙2 = 1.50 lb of Cl ×
2𝐶𝑙
= 1.50 lb of Cl × 208.23
(2)(35.45)
= 4.41 lb

c. The weight of oxalic acid (H2C2O4∙2H2O) in milligrams needed to precipitate the calcium in a 0.5000
g sample of phosphate rock of the composition Ca3(PO4)2.

𝐻2𝐶2𝑂4 = 78.01
2𝐻2𝑂 = 36
𝐶𝑎3(𝑃𝑂4)2 = 310.18

Weight of 𝑜𝑥𝑎𝑙𝑖𝑐 𝑎𝑐𝑖𝑑 = 0.5000 g of 𝐶𝑎 (𝑃𝑂


3
)4×2 (78.01)(36)
310.18
1000 𝑚𝑔
= 4.527 ×
1𝑔
= 4527 mg

d. The weight of pyrites, FeS2, in kilograms that must be burned to produce 3.60 kg sulfuric acid.

𝐹𝑒𝑆2 = 119.95
𝐻2𝑆𝑂4 = 98.05
2
Weight of pyrites = 3.60 kg of sulfuric acid × 𝐹𝑒𝑆
𝐻2𝑆𝑂4
= 3.60 kg of sulfuric acid × 119.95
98.05
= 4.404 kg

e. The milligrams of Mn3O4 that can be obtained by strongly heating 0.2500 g MnO2.

𝑀𝑛3𝑂4 = 228.82
𝑀𝑛𝑂2 = 86.94
3𝑂4
Weight of𝑀𝑛3𝑂 4= = 0.2500 g of 𝑀𝑛𝑂 × 𝑀𝑛
3𝑀𝑛𝑂2
= 0.2500 g of 𝑀𝑛𝑂2 × 228.82
(3)(86.94)
1000 𝑚𝑔
= 0.2193 g ×
1𝑔
= 219.3 mg

3. A 0.8000 g sample pyrolusite (MnO2) yielded 1.282 g Mn2P2O7. What is the percentage purity of
the ore?

𝑀𝑛𝑂2 = 86.94
𝑀𝑛2𝑃2𝑂7 = 283.82
2
Weight of 𝑀𝑛𝑂2 = 1.282 g 𝑀𝑛2𝑃2𝑂7 × 2𝑀𝑛𝑂
= 1.282 g 𝑀𝑛 𝑃 𝑂 (2)(86.94)
𝑀𝑛2𝑃2𝑂7 227 × 283.82
= 0.7854 g
= 0.8000 𝑔 × 100
0.7854 g
𝑝𝑢𝑟𝑒
% purity = = 98.17 %
𝑖𝑚𝑝𝑢𝑟𝑒 × 100

4. What is the percentage purity of a sample of Al2(SO4)3 if a 0.5000 g sample produced a precipitate of
BaSO4 weighing 1.000 g?

𝐴𝑙2(𝑆𝑂4)3 = 342.11
𝐵𝑎𝑆𝑂4 = 233.35
𝑙2(𝑆𝑂4)3
Weight of 𝐴𝑙2(𝑆𝑂 4) =3 𝐴 × 1.000𝑔 𝐵𝑎𝑆𝑂
3𝐵𝑎𝑆𝑂4 𝑝𝑢𝑟𝑒
% purity = × 100
𝑖𝑚𝑝𝑢𝑟𝑒
342.11
=(3)(233.35) × 1.000𝑔 𝐵𝑎𝑆𝑂4 = 0.5000 𝑔 × 100
0.4887 g

= 0.4887 g = 97.74
%

5. A 2.350 g sample of K2CrO4 yielded an ignited precipitate of Cr2O3 which weighed 0.9055 g. Calculate
the percentage Cr and the percentage purity of the salt.

Percentage Cr
Purity of Salt
Weight of Cr = 0.9055 g 𝐶𝑟2𝑂3 × 2 𝐶𝑟
2𝐶𝑟𝑂4
𝐶𝑟2𝑂3 Weight of 𝐾2𝐶𝑟𝑂 4= 0.9055 g 𝐶𝑟 𝑂2 3× 2 𝐾
= 0.9055 g 𝐶𝑟2𝑂3 × 2 (52)
(2) (194.2)
𝐶𝑟2𝑂3
152 = 0.9055 g 𝐶𝑟2𝑂3 ×
= 0.6196 g 152
= 2.314 g
pure
% Purity = × 100
0.6196 g
% Cr = × 100 𝑖𝑚𝑝𝑢𝑟𝑒
2.350 𝑔
2.314 g
= 26.37 % Cr = 2.350 𝑔 × 100
= 98.47 %

6. A 0.8050 g sample of brass, on analysis, yields 0.2537 g SnO2, 1.0752 g Zn2P2O7, and 0.1571 g
Cu. Calculate the percentage of copper, tin, and zinc in the sample.
Cu = 63.55 g/mol
SnO2 O = 7 X 16 = 112
Sn = 1 X 118.71 = 118.71 Zn2P2O7 = 304.7 g/mol
O = 2 X 16 = 32
SnO2 = 150.71 g/mol

Zn2P2O7
Zn = 2 X 65.38 = 130.76
P = 2 X 30.97 = 61.94
537g X Sn
SnO2
Sn = = 0.2537g X 118.71g/mol
0 150.71g/mol
. = 0.1998g (100)
2 0.8050g
Sn = 24.82%
Zn = 1.0752g X Zn Cu = 0.1571g X Cu
Zn2P2O7 Cu
= 1.0752g X 130.76g/mol = 0.1571g X 63.55g/mol
304.7g/mol 63.55g/mol
= 0.4615g (100) = 0.1571g (100)
0.8050g 0.8050g
Zn = 57.32% Cu = 19.52 %

7. An impure sample of Na2SO4 weighed 1.562 g. A BaSO4 precipitate from this sample weighed 2.496 g.
Calculate the percentage of sulfur and the percentage purity of salt.

% Sulfur = wt of precipitate X (g sought/g precipitate) (100)


Weight of sample
= 2.496g X (32.065g / 233.4 g) (100)
1.562g
= 21.95%

BaSO4 Na2SO4
Ba = 1 X 137 = 137 Na = 2 X 23 = 46
S = 1 X 32 = 32 S = 1 X 32 = 32
O = 4 X 16 = 64 O = 4 X 16 = 64
BaSO4 = 233g/mol Na2SO4 = 142 g/mol

2.496g BaSO4 X mole BaSO4 X 1 moleNa2SO4 X 142g = 1.521g Na2SO4


233g BaSO4 1mole BaSO4 mole Na2SO4

% purity = mass of pure substance (100)


mass of impure substance
= 1.521g Na2SO4 (100)

1.562g Na2SO4

= 97.39%

8. What is the percentage of Fe3O4 in an ore sample which weighed 0.5350 g? The sample was dissolved by
fusion with KHSO4, oxidized by Br2 water and the iron was precipitated as hydrous ferric oxide. The ignited
ferric oxide weighed 0.5178 g.

Ore sample = 0.5350g


Ferric oxide =0.5178g
Fe2O3 Fe3O4
Fe = 2 X 56 = 112 Fe = 3 X 56 = 168
O = 3 X 16 = 48 O = 4 X 16 = 64
Fe2O3= 160 g/mol Fe3O4 = 232 g/mol
0.5178g Fe2O3 X mole Fe2O3 X 2 mole Fe3O4 X 232g = 0.50112g Fe3O4
160g Fe2O3 3mole Fe2O3 mole Fe3O4

0.50112 g X 100 = 93.55%


0.5350

9. A 0.8500 g sample pyrites, FeS2, was fused and the sulfur oxidized to SO4-2. The precipitate of BaSO4
weighed 1.4300 g. What is the percentage of the pyrites in the ore?

FeS2 BaSO4
Fe = 1 X 56 = 56 Ba = 1 X 137 = 137
S = 2 X 32 = 64 S = 1 X 32 = 32
FeS2= 120 g/mol O = 4 X 16 = 64
BaSO4 = 233 g/mol

1.4300g BaSO4 X mole BaSO4 X 1 mole FeS2 X 120g = 0.3682g FeS2


233g BaSO4 2mole BaSO4 mole FeS2

0.3682 g X 100 = 43.32%


0.8500 g

10. A chromium ore was brought into solution by an oxidizing flux. 0.5000 g of the ore produced
a precipitate of BaCrO4 weighing 0.5000 g. What is the percentage of Cr2O3 in the ore?

BaCrO4 Cr2O3
Ba = 1 X 137 = 137 Cr = 2 X 52 = 104
Cr = 1 X 52 = 52 O = 3 X 16 = 48
O = 4 X 16 = 64 Cr2O3 = 152 g/mol
BaCrO4 = 253 g/mol

0.5000g BaCrO4 X mole BaCrO4 X 1 mole Cr2O3 X 152g = 0.150176g Cr2O3


253g BaCrO4 2mole BaCrO4 mole Cr2O3

0.150176 g X 100 = 30%


0.5000 g

11. A sample of rock taken for analysis weighs 1.000 g on an air-dried basis. After drying for one hour
at 110o C the sample weighs 0.9437 g. The calcium is precipitated as oxalate weighed as CaSO4; this weighs
0.5000 g. The magnesium is precipitated as MgNH4PO4 which ignited to 0.5000 g Mg2P2O7. Find the
percentages of CaO and MgO on an oven-dried basis and the percentages of these as well as H2O on air-dried
basis.

* mm of CaO  Ca - 40 * mm of CaSO4  Ca - 40 x 1 = 40
O - 16 O - 16 x 4 = 32
56g/mol S - 32 x 1 = 64
136g/mol
* mm of MgNH4PO4  Mg - 24.30
N - 14 x 1 = 14
H -1 x4=4
P - 30.97 x 1 = 30.94
O - 16 x 4 = 64
137.27 g/mol
* mm of Mg2P2O7  Mg - 24.30 x 2 = 48.60
P - 30.97 x 2 = 61.94
O - 16 x 7 = 112
222.54g/mol
*mm of MgO  Mg - 24.30
O - 16
40.30 g/mol
 Amount of CaO
56.08𝐶𝑎𝑂
0.5000g CaSO4 x = 0.2059𝑔 CaSO4
136.15𝐶𝑎𝑆𝑂4

 Amount of MgO
2 (40.31 𝑔 𝑀𝑔𝑂)
0.500m Mg2P2O7 x = 0.1811𝑔 MgO
222.56 Mg2P2O7

 On oven-dried basis
𝑎𝑚𝑜𝑢𝑛𝑔 𝑜𝑓 𝐶𝑎𝑂
a. % weight CaO =
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 100
0.2059 𝑔
= 0.9437 𝑔 𝑥 100
= 21.82 %
𝑎𝑚𝑜𝑢𝑛𝑔 𝑜𝑓 𝑀𝑔𝑂
b. % weight MgO =
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑥 100
𝑠𝑎𝑚𝑝𝑙𝑒

= 0.9437 𝑔 𝑥 100
0.1811 𝑔

= 19.19 %
 On air-dried basis
𝑎𝑚𝑜𝑢𝑛𝑔 𝑜𝑓 𝐶𝑎𝑂
c. % weight CaO = 𝑥 100
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓
𝑠𝑎𝑚𝑝𝑙𝑒
0.2059 𝑔
= 1.000 𝑔 𝑥 100
= 20.59 %
𝑎𝑚𝑜𝑢𝑛𝑔 𝑜𝑓 𝑀𝑔𝑂
d. % weight MgO = 𝑥 100
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓
𝑠𝑎𝑚𝑝𝑙𝑒

= 0.9437 𝑔 𝑥 100
0.1811 𝑔

= 18.11%
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐻20
e. % weight H2O = 𝑥 100
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
1.000 𝑔−0.9837 𝑔
= 1.000𝑔 𝑥 100
= 5.630 %

12. In a steel analysis the CO2 from the combustion of carbon is absorbed in “Ascarite”. I the gain in weight
of the absorbent for a 0.5000 g sample of steel is 15.6 mg, what is the percentage of C in the steel?
* mm of CO2  C - 12 x 1 = 12 * mm of C  C – 12g/mol
O - 16 x 2 = 32
44g/mol

𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 𝑥 (𝑔 𝑠𝑜𝑢𝑔ℎ𝑡/𝑔 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒)


a. % weight C = 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 100
0.156𝑔 𝑥 (12 𝑔/𝑚𝑜𝑙/44 𝑔/𝑚𝑜𝑙)
= 0.5000 𝑔 𝑥 100
= 0.851 %

13. A 0.5000 g sample of FeO is ignited toFe2O3; what is the percentage gain in weight?

2FeO + ½ O2  Fe2O2
* mm of FeO  Fe- 55.85
O - 16
71.85 g/mol
* mm of Fe2O3  Fe- 55.85 x 2 = 111.7
O - 16 x 3 = 48
159.7 g/mol
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 𝑚𝑚 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒
a. weight of Fe2O3 = 𝑅 𝑥 𝑚𝑚 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
0.500𝑔 𝑥 (159.7𝑔/𝑚𝑜𝑙)
= 2 𝑥 71.85 𝑔
= 0.55567g
𝑛𝑒𝑤 𝑤𝑒𝑖𝑔ℎ𝑡−𝑜𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡
b. percent gain = 𝑜𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑤𝑒𝑖𝑔ℎ𝑡 𝑥 100
0.55567𝑔 −0.5000 𝑔
= 0.5000 𝑔 𝑥 100
= 11.13%

14. A 0.7650 g sample of clay, containing 20.50 percent moisture, gave a precipitate of
potassium perchlorate weighing 0.3822 g. What is the percentage of K2 in the clay on a dry basis?

* mm of KClO4  K – 39.09 x 1 = 39.09


Cl - 35.45 x 1 = 35.45
O - 16 x 4 = 64
138.54 g/mol
* mm of K2O  Fe- 39.09 x 2 = 78.18
O - 16 x 1 = 16
94.18
 Amount of K2O
94.2 𝑔 𝐾2𝑂
0.3822 g KClO4 x = 0.1299 𝑔 K2O
138.55 𝑔 𝐾𝐶𝑙𝑂4

 Amount of sample on a dry basis


Original weight of sample – amount of
moisture 0.7650g – 0.2050 (0.7650 g) = 0.6082
g
𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐾2𝑂 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
 % weight of K2O =
𝑥 100
0.1299 𝑥 100
=
𝑔
0.6082 𝑔
= 21.36 %

15. A limestone sample weighing 0.7735 g gave a precipitate of CaC2O4 which was ignited to CaO and
weighed 0.3135 g.
a. Express the percentages of the following in the dolomite: CaO, CaCO3, and Ca2Si2O7, on the
assumption that all the calcium in the rock is present as the specified constituent.

* mm of CaC2O4  Ca - 40.08 x 1 = 40.08


C - 12 x 2 = 24
O - 16 x 4 = 64
128.08 g/mol
* mm of CaO  Ca - 40.08
O - 16
56.08 g/mol
* mm of CaCO3  Ca - 40.08 x 1 = 40.08
C - 12 x 1 = 12
O - 16 x 3 = 48
100.08 g/mol
* mm of CaSiO3  Ca - 40.08 x 1 = 40.08

Si - 20.08 x 1 = 28.08
O - 16 x 3 = 48
116.16 g/mol
* mm of Ca2Si2O7 Ca - 40.08 x 2 = 80.16
Si - 20.08 x 2 = 56.16
O - 16 x 7 = 112
248.32 g/mol
a.1. CaO

𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒 𝑥𝑅


* 𝐺𝐹 = 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
56.08 𝑔/𝑚𝑜𝑙
= 128.08 𝑔/𝑚𝑜𝑙 𝑥 1/4
= 0.109
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 𝑥 𝐺𝐹
* % of analyte = 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 100
0.3135 𝑥 𝑥 100
=
0.109
0.7735
= 4.42%

a.2. CaCO3
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒
* 𝐺𝐹 = 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 𝑥𝑅
100.08
= 128.08 𝑔/𝑚𝑜𝑙 𝑥 1/4
= 0.195
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 𝑥 𝐺𝐹
* % of analyte = 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 100
=
0.3135 𝑥 𝑥 100
0.195
0.7735
= 7.90%
a.3. CaSiO3
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒
* 𝐺𝐹 = 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 𝑥𝑅
116.16
= 128.08 𝑔/𝑚𝑜𝑙 𝑥 3/4
= 0.680
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 𝑥 𝐺𝐹
* % of analyte = 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 100
0.3135 𝑥 0.680
= 0.7735 𝑥 100
= 27.56%
a.4. Ca2Si2O7
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒 𝑥𝑅
* 𝐺𝐹 = 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
248.32
= 128.08 𝑔/𝑚𝑜𝑙 𝑥 1/2
= .99
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 𝑥 𝐺𝐹
* % of analyte = 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 100
0.3135 𝑥 . 𝑥 100
=
99
0.7735
= 40.12%

b. What would the ignited precipitated have weighed had it been ignited to: CaCO3, CaSO4?

b.1.weight of CaC2O4 ignited to CaCO3


*weight of CaCO3
weight of analyte = weight of precipitate – GF
= 0.3135 g – 0.195
= 0.1185
* weight of CaC2O4
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 𝑚𝑚 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒
weight of FeO = 𝑅 𝑥 𝑚𝑚 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
0.7735𝑔1 𝑥 (108.08𝑔/𝑚𝑜𝑙)
= 𝑥 128.08 𝑔
4
= 2.61 g

weight of CaC2O4 ignited to CaSO4


b.2.
* mm of CaSO4  Ca - 40.08 x 1 = 40.08
S - 32.06 x 1 = 32.06
O - 16 x 4 = 64
136.14g/mol

* weight of CaC2O4
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 𝑚𝑚 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒
weight of CaC2O4 = 𝑅 𝑥 𝑚𝑚 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒
0.7735𝑔 𝑥 (136.14𝑔/𝑚𝑜𝑙)
= 1 𝑥 128.08 𝑔
= 0.822g
16. What weight of sample which contains 56.15 percent Cl was taken for analysis if the precipitated AgCl
weighed 0.5017?

0.5017g AgCl × 𝐼𝑚𝑜𝑙 𝐴𝑔𝐶𝑙 = 3.5𝑥10−3 or 0.0035 mol AgCl


143.32𝑔
Ag + Cl = AgCl
0.035 moles Cl × 35.45𝑔 = -.124 g Cl
𝐼 𝑚𝑜𝑙
100g sample: 56.15g Cl :: X grams sample : 0.124g Cl
100𝑔 𝑠𝑎𝑚𝑝𝑙𝑒 𝑥 0.124𝑔 𝐶𝑙
x= 56.15𝑔 𝐶𝑙

x = 56.15 = 0.2208 or 0.2210g sample


12.4

B. Calculations of Volumetric Analysis


(Normality of Solutions)
17. Construct a table showing for HCl, NaOh, H2SO4, Na2CO3 and BaO:

Equivalent Weight Milliequivalent weight 0.15N (g) 0.15N (mg) 0.15M (mg)
HCl 36.46g 36460mg 5.47g/L 5.5mg/L 5.5mg/mL
NaOH 40.00g 40000mg 6g/L 6mg/L 6mg/mL
𝐻2𝑆𝑂4 49.04g 49040mg 14.7g/L 7.4mg/L 14.7mg/mL
𝑁𝑎2𝐶𝑂3 53.0g 53000mg 15.9g/L 8mg/L 15.9mg/mL
BaO 77.0g 77000mg 22.95g/L 11.6mg/L 22.95mg/L

𝑀𝑜𝑙 𝑤𝑡 (𝑔 /𝑚𝑜𝑙 )
Eqwt = 𝑁𝑜.𝑜𝑓 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑐ℎ𝑎𝑟𝑔𝑒𝑠𝑠 (𝑒𝑞 /𝑚𝑜𝑙)

a. Equivalent weight
36.46 g/mol
HCl H=1𝑥1 =1
= 36.46 gram equivalent weight
35.46 1 eq/mol
Cl = 35 x 46 𝑥1 =
36.46 g/mol

40 g/mol
NaOH Na = 23 𝑥 1 = 23 = 40 gram equivalent weight
1 eq/mol
O = 16 𝑥 1 = 16
1
H=1x1=
40 g/mol

H2SO4 H=1𝑥2=2
S = 32 𝑥 1 = 32 98.08 g/mol
= 49.04 gram equivalent weight
64 2 mol
O = 16 x 4 =
98.08 g/mol

Na2CO3 Na = 23 𝑥 2 = 46 106.0 g/mol


= 53.0 gram equivalent weight
2
C = 12 𝑥 1 = 12
48
O = 16 x 3 =
106.0 g/mol

BaO Ba = 138 𝑥 1 = 138


O = 16 x 1 = 16 154 g/mol
154 g/mol = 77.0 gram equivalent weight
2

b. Milliequivalent weight
1𝐸𝑞 = 1000 𝑚𝐸𝑞

HCl = 36.46 𝑥 1000 = 36460


NaOH = 40 𝑥 1000 = 40000
H2SO4 = 49.04 𝑥 1000 = 49040
Na2CO3 = 53.0 𝑥 1000 = 53000
BaO = 77.0 𝑥 1000 = 77000
c. Weight of solute in grams per liter of 0.15 N solution
𝑋
HCl = 0.15 N = 𝑋
36.45 g/mol = = (0.15 𝑁)(1𝐿)
36.45 g/mol

1𝐿 𝑥 = (0.15 𝑁) (1𝐿) (36.45 𝑔/𝑚𝑜𝑙)


𝑥 = 5.47g

𝑋 𝑋 = (0.15 𝑁)(1𝐿)
NaOH = 0.15 N = =
40 g/mol 40 g/mol

1𝐿 𝑥 =𝑥 =6g(0.15 𝑁) (1𝐿) (40 𝑔/𝑚𝑜𝑙)


𝑋
𝐻 𝑆𝑂 𝑋 = (0.15 𝑁)(1𝐿)
= 0.15 N = =
2 4 98 g/mol
98 g/mol
𝑥 = (0.15 𝑁) (1𝐿) (98 𝑔/𝑚𝑜𝑙)
1𝐿
𝑥 = 14.7g

𝑋
𝑁𝑎2𝐶𝑂3 = 0.15 N = 𝑋
= = (0.15 𝑁)(1𝐿)
106 g/mol 106 g/mol

1𝐿 𝑥 = (0.15 𝑁) (1𝐿) (106 𝑔/𝑚𝑜𝑙)


𝑥 = 15.9g

𝑋
BaO = 0.15 N = = 𝑋
153 g/mol = (0.15 𝑁)(1𝐿)
153 g/mol
1𝐿 𝑥 = (0.15 𝑁) (1𝐿) (153 𝑔/𝑚𝑜𝑙)
𝑥 = 22.95g

d. Weight of solute in milligrams per milliliter of 0.15 N solution

𝐻𝐶𝑙 = 36.45 𝑔/𝑚𝑜𝑙


= 0.15 𝑁 𝑥 36.45 g/eq 𝑥 1𝐿
= 5.5 g/L
5.5 g/L 𝑥 1000mg/1g x 1L/1000𝑚𝐿
= 5.5 mg/mL

𝑁𝑎𝑂𝐻 = 40 𝑔/𝑚𝑜𝑙
= 0.15 𝑁 𝑥 40 g/eq 𝑥 1𝐿
= 6 g/L
6 g/L 𝑥 1000mg/1g x 1L/1000𝑚𝐿
= 6 mg/mL
𝐻2𝑆𝑂4 = 98.08 𝑔/𝑚𝑜𝑙
= 0.15 𝑁 𝑥 49.07 g/eq 𝑥 1𝐿
= 7.4 g/L
7.4 g/L 𝑥 1000mg/1g x 1L/1000𝑚𝐿
= 7.4 mg/mL
𝑁𝑎2𝐶𝑂3 = 106.0 𝑔/𝑚𝑜𝑙

= 0.15 𝑁 𝑥 53.0 g/eq 𝑥 1𝐿


= 8 g/L
8 g/L 𝑥 1000mg/1g x 1L/1000𝑚𝐿
= 8 mg/mL

e. Weight of solute in milligrams per milliliter of 0.15 M solution

𝐻𝐶𝑙 = 36.46 𝑔/𝑚𝑜𝑙


m (HCl) = 𝑛𝑀 = (0.15 𝑚𝑜𝑙) (36.45 g/mol)
= 5.47 = 5.5 g HCl per L

5.5 g/L 𝑥 1000mg/1g x 1L/1000𝑚𝐿


6 g/L 𝑥 1000mg/1g x 1L/1000𝑚𝐿
= 5.5 mg/mL

= 6 mg/mL
𝑁𝑎𝑂𝐻 = 40 𝑔/𝑚𝑜𝑙

m (NaOH) = 𝑛𝑀 = (0.15 𝑚𝑜𝑙) (40 g/mol)


= 6 g NaOH per L

𝐻2𝑆04 = 98.08 𝑔/𝑚𝑜𝑙 𝑁𝑎2𝐶𝑂3 = 106.0 𝑔/𝑚𝑜𝑙


m (H2SO4) = 𝑛𝑀 = (0.15 𝑚𝑜𝑙) (98 g/mol) m (Na2CO3) = 𝑛𝑀 = (0.15 𝑚𝑜𝑙) (106 g/mol)
= 14.7 g H2SO4 per L = 15.9 g Na2CO3 per L
14.7 g/L 𝑥 1000mg/1g x 1L/1000𝑚𝐿
= 14.7 mg/mL 15.9 g/L 𝑥 1000mg/1g x 1L/1000𝑚𝐿

= 15.9 mg/mL

18. Use molecular weights rounded to the nearest whole number and solve the following problems
mentally to establish the fundamental concepts of stoichiometric calculations and the selection of units.
a. How many moles of NaOh are present in 1700 ml 0.2 M solution?

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑀= 𝑛
𝑐= 𝑚𝑜𝑙𝑒𝑠
𝑙𝑖𝑡𝑒𝑟𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑣 𝑛 = 0.2 ⦁ 1.7 L
𝐿
𝑛=𝑐⦁𝑣
1𝐿
1700𝑚𝐿 ⦁ = 1.7 𝐿
103 𝑚𝐿
𝑛 = 0.34 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎𝑂𝐻
b. How many milliequivalents of H2SO4 are present in 50 ml 0.4 N solution?

𝐹𝑜𝑟𝑚𝑢𝑙𝑎: 𝑀𝐸𝑄 𝑠𝑜𝑙𝑢𝑡𝑒 = 𝑣(𝑚𝐿) 𝑥 𝑁


50 mL 𝑥 0.4 meq/mL
= 20 meq

c. How many milligrams of KOH are present in 25 ml 0.04 N solution?

𝑀𝑖𝑙𝑙𝑖𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑠𝑜𝑙𝑢𝑡𝑒 = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑖𝑛 𝑚𝑖𝑙𝑙𝑖𝑙𝑖𝑡𝑒𝑟 𝑥 𝑁


𝑚𝑒𝑞
= 25 𝑚𝐿 𝑥 0.04
𝑚𝐿
= 1 meq

𝑊𝑒𝑖𝑔ℎ𝑡 = 𝑀𝑖𝑙𝑙𝑖𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑥 𝑚𝑖𝑙𝑙𝑖𝑔𝑟𝑎𝑚𝑠 𝑝𝑒𝑟 𝑚𝑖𝑙𝑙𝑖𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡


= 1 𝑚𝑒𝑞 𝑥 56 mg/meq
= 56 mg

d. How many grams of HNO3 are present in 1500 ml 0.2 F solution?

𝐻𝑁𝑂3 = 63 𝑔/𝑚𝑜𝑙

1500 𝑚𝐿
1.5 𝐿
𝑋 𝑋
0.2 F = = (0.2 F) (1.5 L)
631.5
g/mol
𝐿 63 g/mol
𝑥= (0.2 𝐹) (1.5 𝐿) (63 g/mol)

𝑥 = 18.9 𝑔

e. 85.5 mg of Ba(OH)2 s dissolved in 500 ml of solution. What is the normality of the solution?

𝐺𝑟𝑎𝑚𝑠 𝑜𝑓 𝑆𝑜𝑙𝑢𝑡𝑒 = 85.5 𝑚𝑔 /1000 = 0.0855 𝑔


𝑁=𝑀⦁n
𝑀𝑊 𝑜𝑓 𝐵𝑎(𝑂𝐻)2 = 171 𝑔/𝑚𝑜𝑙
= 0.001 𝑥 2
0.0855𝑔 1 𝑚𝑜𝑙
𝑀 = 171 𝑔/𝑚𝑜𝑙
x = 0.001
0.5𝐿 𝐿
= 0.002 N
f. How many milligrams of Na2CO3 will react with 50 ml 0.2 N HCl?

𝐵𝑎𝑙𝑎𝑛𝑐𝑒𝑑 𝑅𝑒𝑎𝑐𝑡𝑖𝑜𝑛

𝑁𝑎2𝐶𝑂3 + 2𝐻𝐶𝑙 2𝑁𝑎𝐶𝑙 + 𝐻2𝑂 + 𝐶𝑂2

𝐻𝐶𝑙 𝐻+ 𝑖𝑜𝑛 0.2 𝑁 = 0.2 𝑀 𝑜𝑟 0.2 𝑚𝑜𝑙/𝐿


1𝐿
50 𝑚𝐿 = = 0.05 L of HCl
1000 𝑚𝐿

0.05 𝐿 = 0.2 𝑚𝑜𝑙 = 0.01 moles of HCl


𝐿
0.01 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻𝐶𝑙
2 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻𝐶𝑙 1 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑁𝑎2𝐶𝑂3 = 0.005 moles of N𝑎2𝐶𝑂3 𝑟𝑒𝑎𝑐𝑡
2 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻𝐶𝑙
𝑀𝑊 𝑜𝑓 N𝑎2𝐶𝑂3 = 105.99 𝑔/𝑚𝑜𝑙
105.99 g/mol 𝑥 0.005 𝑚𝑜𝑙 = 0.530 𝑔 𝑜𝑟 530 𝑚𝑔 N𝑎2𝐶𝑂3 react

g. How many milliliters of 0.1 N NaOH solution will react with 30 ml 0.15 N HCl solution?

𝑁1𝑉1 = 𝑁2𝑉2

(0.1 𝑁) 𝑉1 (0.15 𝑁) (30𝑚𝐿)


0.1 𝑁 = 0.1 𝑁
𝑉1 = 45 𝑚𝐿

h. How many milliliters of 0.025 M Ba(OH)2 solution will react with 50 ml 0.1 N H2SO4?

𝑁1𝑉1 = 𝑁2𝑉2 𝑁1 = 0.025 𝑀 𝐵𝑎 (𝑂𝐻)2

(0.05 𝑁) (𝑉1) (0.15 𝑁 ) (50𝑚𝐿)


(0.05 𝑁) = (0.05 𝑁) 𝑁 = (𝑀) (n)
𝑉1 = 100 𝑚𝐿 = (0.025 𝑀) (2)
= 0.05 𝑀
i. 25 ml 0.2 N KOH reacts with 50 ml H3PO4 solution. What is the normality of the acid solution?

𝑁1𝑉1 = 𝑁2𝑉2
5
(0.02 𝑁) (25 𝑚𝐿) (𝑥) (50 𝑚𝐿) = 0.1 𝑁
=
50 𝑚𝐿 50 𝑚𝐿 50
j. If the titration reaction in (i) is: H3PO4 + 2OH-= HPO4-2 + 2H2O, what is the molarity of the phosphoric
acid solution?

𝑎. ) 𝐻3𝑃𝑂4 𝑑𝑜𝑛𝑎𝑡𝑒𝑑 2 𝑎𝑡𝑜𝑚𝑠 𝑜𝑓 𝐻+

𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 = 0.1 𝑁 = 0.05 M


2

𝑏. ) 𝐻3𝑃𝑂4 + 2𝑂𝐻− = 𝐻𝑃𝑂4−2 + 2𝐻2𝑂

𝐻3𝑃𝑂4 + 2𝐾𝑂𝐻 = 𝐾2𝐻𝑃𝑂4 + 2𝐻2𝑂


𝑀𝑉 = # 𝑚𝑜𝑙

𝐾𝑂𝐻: 0.025 𝑥 0.2 = 0.005 𝑚𝑜𝑙


1 𝑚𝑜𝑙 𝑎𝑐𝑖𝑑 = 2 𝑚𝑜𝑙 𝑏𝑎𝑠𝑒
𝑥 = 0.005 𝑚𝑜𝑙
𝑥 = 0.0025 𝑚𝑜𝑙 𝑎𝑐𝑖𝑑

𝐴𝐶𝐼𝐷: 𝑀𝑉 = # 𝑚𝑜𝑙
0.0025 0.05 𝑥 𝑀
0.05 = 0.05
0.05 = 𝑀
0.05 = 𝑀
19. What is the equivalent weight of:
a. Potassium tetraoxalate, KHC2O4∙H2C2O4∙2H2O, if complete neutralization is assumed?

700.89𝑔/𝑚𝑜𝑙
3 = 233.63g

b. Sodium carbonate if it is titrated to the phenolphthalein end point with HCl? The reaction is Na2CO3
+ HCl = NaCl + NaHCO3.

106𝑔(𝑀𝑊 𝑜𝑓 𝑁𝑎2𝐶𝑂3)
1 = 106g

c. Sodium tetraborate decahydrate if the titration reaction is

Na2B4O7∙10H2O + 2H+ + H2O → 4HBO2 + 2Na+?


381.37𝑔
= 190.69g
2

d. Na3PO4∙12H2O if it is titrated with phenolphthalein as an indicator to form HPO4-2?


380.12𝑔
= 380.12g
1

20. How many grams of solute are in each of the following solutions?
Solution Concentration
a. 2 liters HCl 2.5 N

2.5mol equi.
× 𝟐𝑳 = 5mol equi.
𝑳𝒊𝒕𝒆𝒓𝒔 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏

Molecular weight: 36.45/1 = 36.45 mol equi.


36.45×5= 182.3g
b. 3 liters H2SO4 1.5 N
3mol equi.
𝑳𝒊𝒕𝒆𝒓𝒔 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
× 𝟏. 𝟓𝑳 =4.5mol equi.

Molecular weight: 98/2 (#of replacable hydrogen atoms) =49 mol equi.
49×4.5= 220.5g

c. 150 ml HCl 0.25 N

1L
𝟏𝟓𝟎𝒎𝑳 × =. 𝟏𝟓𝑳
𝟏𝟎𝟎𝟎𝒎𝑳

.25mol equi.
𝑳𝒊𝒕𝒆𝒓𝒔 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 × 𝟏. 𝟓𝑳 = 0.0375mol equi.
Molecular weight: 36.45/1= 36.45g
36.45g×0.0375g = 1.4g

d. 125 ml NaOH 1.5 N

1.5mol equi.
𝑳𝒊𝒕𝒆𝒓𝒔 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 × 𝟎. 𝟏𝟐𝟓𝑳 = 0.1875mol equi.
Molecular weight: 40/1 = 40 mol equi.
40×0.125= 5g

e. 1.5 liters Na2CO3 2.0 N

2 mol equi.
𝑳𝒊𝒕𝒆𝒓𝒔 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 𝟏. 𝟓𝑳
=3 mol equi.
Molecular weight: 106/2 = 53 mol equi.
53g×3g= 159g

21. How many each of the following solutions be prepared?


a. 150 ml 0.1 N NaOH, from solid NaOH.

Equivalent solute= volume in L * Normality


= 0.150L * 0.1N
Equivalent solute= 0.015 eq
Weight in grams= eq * mass
= 0.015 eq * 40 g/eq
Weight in grams = 0.6 g

b. 100 ml 0.1 N NH3, from a 1.1 N solution

Milliequivalent= 100mL * 0.1𝑚𝑒𝑞


𝑚𝐿
Milliequivalent= 10meq
Value required= 10𝑚𝑒𝑞
1.1𝑚𝑒𝑞
𝑚𝑙
Value required = 9.1mL

c. 1.5 liters 0.05 N Ba(OH)2, from solid

BaO Equivalent solute= volume in L * Normality


= 1.5 L * 0.05N
Equivalent solute= 0.075eq
Weight in grams= 0.075eq * 171.34g/mol
Weight in grams = 12.85g

d. 150 ml 0.15 N HCl, from a 12N solution

Milliequivalent= 150mL * 0.15𝑚𝑒𝑞


𝑚𝐿
Milliequivalent= 22.5meq
22.5𝑚𝑒𝑞
Value required= 12𝑚𝑒𝑞
𝑚𝑙
Value required = 1.875mL

22. How much of substance B is needed to react with the given amount of A?

B 80 mg MgO
a. 40.00 ml 0.5000 N H2SO4

b. 106.0 mg Na2CO3
29.44_ ml 0.1000 N HCl for complete neutralization
c. 30.00 ml 0.2000 M H2SO4
60 ml 0.2000 N NaOH
d. 25.00 ml .0.1500 N KOH
45.75 mg benzoic acid
e. 204.2 mg potassium acid
91 ml 0.04000 N KOH
phthalate
f.4.000 meq H2SO4
80 ml 0.0250 M Ba(OH)2
g. 0.5000 g 85.0% H3PO4
88 ml 0.1200 N NaOH if reaction is
solution H3PO4 + OH- = H2PO4- + H2O
Solution:
a) Equivalent solute= 0.040L * 0.5000N
Weight in grams= 3.75𝑥10−3 eq * 122 𝑔𝑟𝑎𝑚𝑠
Equivalent solute= 0.02 eq 𝑒𝑞
Weight in g= 0.02*40
Weight in grams= 0.4575 g
Weight in g= 0.8g
Weight in mg = 80mg Weight in mg = 45.75mg
b) Weight in grams= equivalent solute * molar
mass e) Weight in grams= eq * mass
0.106𝑔 𝑥∗36 0.2042
= 𝑒𝑞∗56=56
56 −3
36𝑔 36 Eq= 3.64𝑥10
X= 2.94𝑥10−3𝑒𝑞 Eq= Volume in L * Normality
Equivalent solute= Volume in L * Normality 3.64𝑥10−3 𝑥∗0.04000
2.94𝑥10−3𝑒𝑞 𝑥∗0.1000 𝑁 0.04000 = 0.04000
=
0.1000𝑁 0.1000 𝑁 X= 0.091 L
X= 0.0294 Volume in mL= 91mL
Volume in mL= 29.44 f) Meq= volume in mL * Normality
𝑁1𝑉1 𝑁2𝑉2 4.00 𝑣𝑜𝑙𝑢𝑚𝑒 𝑖𝑛 𝑚𝐿 ∗0.05𝑁
c) 𝑁2 = 𝑁2 0.05 = 0.05
𝑁1𝑉1 Volume in mL = 80 mL
𝑉2= 𝑁2 g) Weight in grams= eq * mass
2 0.4𝑁∗30 𝑚𝐿 0.5000 𝑒𝑞∗40
𝑉 = 0.2𝑁 40 = 40
Equivalent solute= 3.75𝑥10−3 eq
𝑉2 = 60 𝑚𝐿
d) Equivalent solute= Volume in L * Normality
= 0.025L * 0.1500N
Eq= 0.0125 0.0125
= 0.1200
𝑥∗0.1200
Eq= Volume in L * Normality 0.1200
X= 0.104 L * 0.85
X=0.0884
Volume in mL = 88mL

23. What size sample (to the nearest 0.01 g) should be taken of each of the following, in order that 40.00 ml
0.2000 N acid or base shall be needed for the titration of the sample?

1.00mL acid= 0.2000meq


40.00 mL=8 meq

a. KH(IO3)2

KH(𝐼𝑂3)2 = 8meq * 3902

KH(𝐼𝑂3)2 = 1560mg or 1.56g

b. Na2CO3

𝑁𝑎2𝐶𝑂3 = 8meq * 1062

𝑁𝑎2𝐶𝑂3 = 424mg or 0.42 g

24. How many milligrams of calcite, CaCO3, are needed to neutralize 40.15 ml of 0.0082 N H2SO4? Of
0.0982 M H2SO4?

>Milliequivalents acid= Milliequivalents calcium


carbonate >Milliequivalents acid= Milliequivalents calcium
carbonate
= 40mL * 0.0982 meq/mL
= 40 mL * 0.1964 meq/mL
= 3.93meq
= 7.86 meq
Weight of calcite= 3.93meq * 50.05 mg/meq
Weight of calcite= 7.86meq * 50.05 mg/meq
Weight of calcite= 196.7 mg
Weight of calcite= 393.40 mg

25. What are the normality and molarity of as solution prepared by dissolving 8.050 g Ba(OH)2∙8H2O
in 1500 ml of solution?

Molecular weight of Ba(OH)2 = 171. 34 g/mol


No. of equivalence weight= (171.34 g/mol) / 2
No. of replaceable OH= 2
= 85.5 g/mol
Molarity = 8.050 g X 1 mol of Ba(OH)2 X 1000 ml = 0.0313 M
1500 ml 171.34 g Ba(OH)2 1L

Normality = MXn
= 0.0313 x 2
= 0.0626 N

26. To what volume should 50.00 ml 1.250 N H2SO4 solution be diluted to prepare a 0.8000 N solution?

N1V1 = N2V2
(1.250𝑁)(50.00𝑚𝑙) = (0.8000N) (V2)
(1.250𝑁)(50.00 𝑚𝑙)
(0.8000𝑁) = 𝑉2
= 78.13 ml

27. 35.00 ml H2SO4 solution yields a precipitate of BaSO4 which weighs 0.8000 g. What is the normality of
the acid?

BaSO4 = 137.327+ 32.059+ 16(4)


= 233.386g BaSO4
1 𝑚𝑜𝑙 𝐵𝑎𝑆𝑂4
𝑀𝑂𝐿𝐴𝑅𝐼𝑇𝑌 = 𝑚𝑜𝑙 0.8000𝑔 BaSO4×
× 0.035 𝐿 = 0.098 𝑀
1
𝐿 233.386𝑔 𝐵𝑎𝑆𝑂4
N= M∗ 𝑛
= 0.098 M (2)
= 0.196N

Other solution:
# 𝑒𝑤 1 𝑚𝑜𝑙 𝐻+
𝑁= 1 𝑚𝑜𝑙 𝐻2𝑆𝑂4 233. 386𝑔 𝐵𝑎𝑆𝑂4
𝐿 2 𝑚𝑜𝑙 𝐻+ × 1 𝑚𝑜𝑙 𝐻2𝑆𝑂4 = 116.693
1
× 1𝑒𝑤
0.8000g BaSO4× 1
116.693 × 0.035 𝐿 = 0.196 𝑁

28. 25.00 ml HCl solution is required to react with 0.1854 g of pure Na2CO3. What is the normality of
the acid? 32.16 ml of the acid reacts with 29.65 ml NaOH. What is the normality of the NaOH?

Na2CO3 +2 HCl ===== 2NaCl + H2O + CO2


1 𝑚𝑜𝑙
0.1854 g Na2CO3 ×
× 0.025 𝐿 = 0.0699𝑀
106𝑔 𝑁𝑎2𝐶𝑂3 1

1 𝑚𝑜𝑙 𝐻 + 1𝑚𝑜𝑙 𝐻𝐶𝑙 106 𝑔 𝑁𝑎2𝐶𝑂3


× × = 53 𝑒𝑤
1 2 𝑚𝑜𝑙 𝐻𝐶𝑙 1 𝑚𝑜𝑙 𝐻𝐶𝑙
0.0699 𝑀
N= 53 𝑒𝑤
Acid = 0.1399 N
N1V1 = N2V2
(0.1399 N) (32.16 ml) = (N2) (29.65 ml)
(0.1399 𝑁)(32.16 𝑚𝑙)
(29.65 𝑚𝑙) = N2
Base = 0.1574 N

29. Find the normality of acid and base solution from the
following: Weight Na2CO3 (99.5 % pure) 0.2027 g
Volume HCl 45.50 ml
Volume NaOH (back titration) 3.57 ml
35.05 ml NaOH = 31.03 ml HCl

0.2027 𝑔
mol Na2CO3 (95.5 %) =
106 𝑔/𝑚𝑜𝑙
× 0.995

= 1.90 × 10−3 𝑚𝑜𝑙


35.05 31.03
Excess vol HCl = =
3.57 𝑥

= 3.16 ml
Vol of HCl need to titrate = (45.5 – 3.16) ml
= 42. 34 ml
HCl = 42. 34 ml (M) = mol Na2CO3

1.90 ×10−3 𝑚𝑜𝑙


M HCl = 42.34 𝑚𝑙 × 1000
= 0.045 M HCl
= 0.045 N HCl

0.045 𝑀
NaOH 31.03 𝑚𝑙 𝑀 𝑁𝑎𝑂𝐻
= 35.05 𝑚𝑙

M NaOH = 0.0508 M
= 0.0508 N NaOH

30. 45.00 ml 0.11163 N H2SO4 was added to 0.4000 g of a sample of soda ash which is 67.72 percent
Na2CO3. What volume of 0.1053 N NaOH is required for back titration?

45 ml H2SO4
0.1163 H2SO4 = 0.05815 M
0.4000 g soda ash 67.72%
0.4000 𝑔 ×0.6772
= 106 𝑔/𝑚𝑜𝑙
= 2.555× 10−3
Excess H2SO4 = 2.61675 × 10−3 − 2.555 × 10−3 𝑚𝑜𝑙
= 6.1 × 10−5
Ratio of H2SO4 to NaOH = 2:1
(MNaOH) (XNaOH) = 2(excess H2SO4)
(XNaOH 2 ( 6.1×10−5)
) = 0.1053 𝑀
= 1.1638 × 10−3𝐿
= 1.16 ml

31. A soda-lime sample is 90.0 percent NaOh and 10 percent CaO. If 3.00 g is dissolved in 250 ml, what is
the total normality of the solution as a base? How many milliliters of 0.5100 N H2SO4 would be required to
titrate 100 ml of the solution?
1 𝑚𝑜𝑙 0.03125 𝑚𝑜𝑙
3g x 96 x 0.25 𝐿
= 0.125 N
1𝑔

N1V1=N2V2
0.125 (250 𝑚𝑙)
0.51 = 61.274 ml

32. Compute the normality and molarity of each of the following solutions:
a. HCl, of density 1.12, containing 24.0% HCl by weight

1𝑚𝑜𝑙 𝐻𝐶𝑙 0.67 𝑚𝑜𝑙


24g HCl x36𝑔 𝐻𝐶𝑙 = 0.059 𝐿 = 7.52 M
N= M x n
= (7.52 M) (1)
= 7.52 N

b. HNO3, of density 1.42, containing 72% HNO3 by weight

1 𝑚𝑜𝑙 𝐻𝑁𝑂3 1.14 𝑚𝑜𝑙


72 HNO3 x 63𝑔 𝐻𝑁𝑂3
= 0.070 𝐿
= 16.28 M
N= M x n
= (16.28 M) x (1)
=16.28 N

c. H2SO4, of density 1.83, containing 95% H2SO4 by weight

1 𝑚𝑜𝑙 𝐻2𝑆𝑂4 0.97 𝑚𝑜𝑙


95g H2SO4 x = = 17.96 M
98𝑔 𝐻2𝑆𝑂4 0.054 𝐿
N= M x n
= (17.96 M) (2)
=35.92 N

d. H2SO4, of density 1.8002, containing 71.84% SO3 by weight

1 𝑚𝑜𝑙 𝐻2𝑆𝑂4 0.75 𝑚𝑜𝑙


71.83g H2SO4 x x =13.27 M
98𝑔 𝐻2𝑆𝑂4 0.55 𝐿
N= M x n
= (13.27 M) (2)
= 26.54 N

e. NH3, of density 0.89, containing 30% NH3 by weight

1 𝑚𝑜𝑙 𝑁𝐻3 1.76 𝑚𝑜𝑙


30g NH3 x x = 15.71 M
17𝑔 𝑁𝐻3 0.112 𝐿
N= M x n
= (15.71 M) (1)
=15.71 N

f. NaOH, of density 1.10, containing 10% NaOH by weight


1 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻 0.25 𝑚𝑜𝑙
10g NH3 x 40𝑔 𝑁𝑎𝑂𝐻 x 0.090 𝐿 = 2.78 M
N= M x n
= (2.78 M) (1)
=2.78 N

33. How many milliliters of an HNO3 solution whose density is 1.389 g per milliliter and which contains
63.00 % acid by weight are requires to prepare 1500 ml 0.3000 N solution?

1000 𝑚𝑙
1L x 1𝐿 x 1.389 𝑔 x 0.63= 875.07 g
𝑚𝑙

875.07𝑔
M= 61.004𝑔/𝑚𝑜𝑙 13.89 𝑚𝑜𝑙
x 1𝐿 = 13.89 M
N= M x n
= (13.89 M) (1)
= 13.89 N
N1V1= N2V2

(0.3000 𝑁)(1.5 𝐿)
(V1) = 13.89 𝑁

= 32. 4 ml

34. A solution of sulfuric acid has a density of 1.250 g per milliliter and contains 49.00 % H2SO4 by weight.
a. How many milliliters of this acid are needed to prepare 250 ml 0.2000 N solution?
1.250 𝑔 612.5 g
1000 ml x x 0.49 x = 6.25 mol
𝑚𝑙 98.07 𝑔/𝑚𝑜𝑙
6.25 𝑚𝑜𝑙
M= = 6.25 M
1𝐿
N= M x n
=(6.25 M) (2)
= 12.5 N
N1V1= N2V2
(0.25 𝐿)(0.2000 𝑁)
V1= 12.5 𝑁 = 4 ml

b. 250 ml of the concentrated acid is diluted to 2.000 liters. What is the normality of the diluted solution?

(250 𝑚𝑙)(12.5 𝑁) 2000 𝑚𝑙


2000 𝑚𝑙 = 2000 𝑚𝑙 = 1.5625 N

35. What is the normality of a sulfuric acid solution of density 1.2185 g per milliliter at 20oC? (Refer to
a handbook for the necessary data to solve this problem.)

N= 1000 ml x 1.2185 𝑔 x 1 = 1218.5g


𝑚𝑙
1218.5 𝑔
= 12.42 mol
98.07 𝑔/𝑚𝑜𝑙
12.42 𝑚𝑜𝑙
M= = 12.42 M
1𝐿
N= M x n
= (12.42 M) (2)
= 24.84 N

36. Express titers as follows:


a. 0.1500 N HCl in terms of : NaO, Na2O, BaO, K2CO3

mg
Titer( )
mL
N = Equivalent
weight
Titer = N(Equivalent Weight)
1. NaOH = (0.1500N)(40.00 meq)
mL

NaOH = 6 mg
mL

2. Na20 = (0.1500N) (30.85 meq)


mL

𝑁𝑎2𝑂=4.63 𝑚𝑔𝑚𝑙
mg
Na2 O = 4.63
mL
3. BaO = (0.1500N)(153.37 meq)
mL

BaO = 23 mg
mL

4. K 2CO = (0.1500N)(69.1 meq)


mL
K 2CO = 10.37 mg
mL

b. 0.1200 N NaOH in terms of : HCl, H2SO4, potassium acid phthalate.

1. HCl = (0.1200N)(36.46 meq)


mL

HCl = 4.38 mg
mL

2. H2SO = (0.1200N)(49.04 meq)


mL
mg
H2SO = 5.88
mL
3. C8H5KO4 = (0.1200N)(204.22 meq
m
)

C8H5KO4 = 24.51 mgm

37. What is the normality of a H2SO4 solution whose Ba(OH)2 titer is 1.714 mg?

mg
Titer( )
Molar Mass
mL
N = Equivalent weight Equivalent weight = # of equivalence
Ba(OH)2 = 137.3 + (2 × 16) + (2 × 1) 171.3 g Ba(OH)2
Equivalent weight =
= 171.3 g Ba(OH)2 2
= 85.65 meq
1 .714
mL
N=
mg

mg
85.65 mL
N = 0.02001

C. Calculations based on Molarity of Solutions


38. How many milliliters of NH3 (density= 0.91 g/ml, 25% NH3) are needed to precipitate the iron as
hydrated ferric oxide from a 0.1262 g sample of FeCl2?

FeCl2 + 2(NH3 ∙ H2O) → Fe(OH)2 + 2NH4Cl


g
0.91 227.5g NH3
× 1000mL × 0.25 = 227.5g NH3 moles NH 3 = = 13.38 mol NH3
mL 1molFeCl 2 17g NH3
1000mL
0.1262 gFeCl × 2mol(NH3 ∙ H2O) 1LNH3 × = 0.15mL NH
2 × × 3
126.9gFeCl2 1molFeCl2 13.38 molNH3 1L

39. How many milliliters of 0.1 M NH3 solution are needed to precipitate the iron as ferric hydroxide from a
2 g sample of ore which is approximately 80% Fe3O4?

Fe3+ + 3NH3 + 3H2O → Fe(OH)3 + 3NH4


3O 4
moles Fe3O4 = 2.00g×0.80Fe
g
231.54 Fe O
= 6.91 × 10−3 mol Fe3O4
3 4
mol
3+
moles Fe = 3 moles Fe × 6.91 × 10−3 = 0.02073 moles

3mol(0.02073mol Fe3+)
mol
0.1 NH = 0.6219L NH3
L 3
1000mL
0.6219L × = 621.9 mL NH
3
1L

40. If the iron in 0.1500 g sample of ore is reduced and subsequently requires 15.03 ml 0.02000 M KMnO4
for titration, what is the purity of the ore expressed as percentage of: Fe, FeO, Fe2O3?

KMnO4 +1L
5Fe + 8N → Mn + 5Fe + 4H2O
15.03mL KMnO4 × × 0.0200MKMnO4 × 5mol Fe × 55.85gFe
1000mL
% Fe = × 100
0.1500g sample ore
% Fe = 55.96%
1L
15.03mL KMnO4 × × 0.0200MKMnO4 × 5mol Fe × 71.85gFeO
1000mL
% FeO = × 100
0.1500g sample ore
% FeO = 72%
1L 5
15.03mL KMnO4 × × 0.0200MKMnO4 × mol Fe × 159.7gFe2O3
% Fe2O3 = 1000mL 2
0.1500g sample ore × 100
% Fe2O3 = 80%

41. How many milliliters of a solution which contains 1 g AgNO3 per 20 ml are needed to precipitate the
AgCl from a 0.5000 g sample of BaCl2∙2H2O id a 5% excess is to be used?

1gAgNO⋅3=3g2ANO
20ml=3g2ANO
AgCl=3g2ANO
a⋅(0.5g)=0.5aga⋅(0.5g)=0.5ag
BaCl⋅2⋅(2H25%) = 0.2Ba2ClH2
ml

42. If a 10% excess is to be used, how many milliliters of 0.15 M AgNO3 are needed to precipitate the AgCl
from a sample which weighs 0.5000 g and contains 3 mM ZnCl2?

a10%=0.1
0.15MAgNO⋅3=0.45MAgNO
AgCl=0.45M AgNO
0.5g=0.45M AgNO
3mMZnCl⋅2 = 6mMZnCl ml

43. How much 0.15 M Na2SO4= solution is needed to precipitate the BaSO4 from the sample of problem 41
if no excess is to be used?

0.15MNa2SO4=solution
BaSO⋅ 4 = 4 BaSO
1g AgNO⋅3 = 3g2 ANO
20ml = 3g2 ANO ml

44. Find the number of milliliters of a solution which contains 0.2000 mole BaCl2 in 500 ml solution that is
needed to precipitate SO4-2 as BaSO4 from 3 mM Al2(SO4)3?

Al2(SO4)3 + 3BaCl2 = 3BaSO4 + 2AlCl3


C(BaCl2) = 0.2/0.5 = 0.4 M
n(SO42-) = 3*3/1000 = 0.009 mol
n(BaCl2) = 0.009 mol
V(BaCl2) = 0.009/0.4 = 0.0225 L = 22.5 mL

45. 25 ml AgNO3 reacts with 5 mM NaCl; 35 ml of the silver solution is required to titrate a sample of
ZnCl2∙6H2O. How many milligrams of the hydrate are present in the sample?

25 ml AgNO3 reacts with 5 mM (Cl-)


25 35
5  x
x = 7 mM.
n(ZnCl2*6H2O) = 7/2 = 3.5 mmol.
m(ZnCl2*6H2O) = 3.5*(65+71+6*18)/1000 = 0.854 g = 854 mg

D. Miscellaneous Problems
46. A sample is known to be NaCL, KCl or MgCl2 or a mixture of these constituents. What is the smallest
volume of .02 M AgNO3 that will insure the complete precipitation of Cl- from a 1 g sample?

0.2 M AgNO3

NaCl + AgNO3 = AgCl + NaNO3


KCl + AgNO3 = KNO3 + AgCl
MgCl + AgNO3 = MgNO3 + AgCl

0.2 𝑚𝑜𝑙 (1 L)(69.87 𝑔) = 13.974 g


𝐿 1 𝑚𝑜𝑙

1 𝑚𝑜𝑙
1 g NaCl x
58.44 0.2
x 1 𝑚𝑜𝑙 x 1 L =
0.0034 𝑚𝑜𝑙 = 3.422313484x10-3 = 3.4x10-3
1𝐿

1 𝑚𝑜𝑙 0.2
1 g KCL x x 0.0027 𝑚𝑜𝑙 = 2.682763246 x 10 -3 = 2.7 x 10 -3
74.55 1 𝑚𝑜𝑙 x1L= 1𝐿
1 𝑚𝑜𝑙 0.2
1 g MgCl x x
0.0021 𝑚𝑜𝑙 = 2.100619683x10-3 L = 2.1 x10-3 L
95.21 1 𝑚𝑜𝑙 x1L= 1𝐿

47. How many milligrams of a 20% by weight solution of (NH4)2Cr2O7 are needed for the precipitation of
the barium as chromate from a 1 g sample of mixture which is 50% Ba(NO3)2 and 50% Sr(NO3)2. The
precipitation reaction is
2Ba+2 + Cr2O7-2 + H2O + OAc- = 2BaCrO4 + HOAc

(NH4)2Cr2O7 = 252.07 g/mol (.20) = 50.414

50.414 g
50% Ba(NO3)2
50% Sr(NO3)2
g NO3 = NO3 in Ba(NO3)2 + NO3 in Sr(NO3)2
62.0049 𝑔/𝑚𝑜𝑙 62.0049 𝑔/𝑚𝑜𝑙
= 0.50 (50.414g)( ) + 0.50 (50.414g)( )
261.337 𝑔/𝑚𝑜𝑙 211.63 𝑔/𝑚𝑜𝑙

= 13.36595146 g = 13. 37 g
= 13370 mg
48. In what proportions would KCl be mixed with NaCl or LiCl to produce a mixture which contains 65% Cl?
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑒 (𝑁𝑎𝐶𝑙)
KCl + NaCl = KNa + 2Cl %(w/w) = x 100
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑒
65% = 132.99 𝑔
65%
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑒
100% = 132.99 𝑔
(65)(132.99)
1 mole KCl x 1 𝑚𝑜𝑙 𝐾𝐶𝑙 = 74.55 g Mass NaCl =
74.55 𝑔/𝑚𝑜𝑙
100
1 moles NaCl x 58.44 𝑔/𝑚𝑜𝑙 = 58.44 g Mass of NaCl = 86.44 g
1 𝑚𝑜𝑙 NaCl
Mass Solution = 132.99 g Mass of KCl = Mass Solution – Mass of NH4Br
= 132.99 – 86.44
Mass of KCl = 46.55 g
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑒 (𝐿𝑖𝐶𝑙)
KCl, LiCl %(w/w) = x 100
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑒
65% = 116.94 𝑔
74.55 𝑔/𝑚𝑜𝑙 = 74.55 g 65%
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑒
1 mole KCl x 1 𝑚𝑜𝑙 𝐾𝐶𝑙 100% = 116.94 𝑔
(65)(116.94)
1 mole LiCl x 1 𝑚𝑜𝑙 𝐾𝐶𝑙 = 42.39 g Mass LiCl =
42.39 𝑔/𝑚𝑜𝑙
100
Mass Solution = 116.94 g Mass of LiCl = 76.01 g
Mass of KCl = Mass Solution – Mass of NH4Br
= 116.94 – 76.01
Mass of KCl = 40.93 g

49. A mixture of 0.5000 g FeO and 0.2500 g Fe2O3 is heated in air (FeO is oxidized to Fe2O3). What is the
weight of the solid? A stream of hydrogen is passed over thee heated solid to reduce the oxide the metallic
iron. What is the weight of the metal?

2Fe + O = Fe2O3
159.69 𝑔 𝐹𝑒2𝑂3
0.5000 g FeO x = 0.557
2(71.844)𝑔 𝐹𝑒𝑂
0.557g Fe2O3 + 0.25 g Fe2O3 = 0.8057 g Fe2O3
2(55.85)𝑔 𝐹𝑒
0.8057 g Fe2O3 x = 0.5636 g Fe
159.69 𝑔 𝐹𝑒2𝑂3

50. A sample is mixture of Mohr’s salt [FeSO4∙(NH4)2SO4∙6H2O] and NH4SO4. A 0.5000 g sample gave a
precipitate of 0.7500 g BaSO4. Calculate the percentage composition of the mixture. What weight of Fe2O3
would be obtained if 0.2000 g of the sample were ignited in air?
When the mixture of mohr's salt and ammonium sulphate reacts with barium chloride, only ammonium sulphate
reacts to form barium sulphate. The reaction being:

Let x be the grams of NH4SO4


.500 – x = grams of Mohr’s Salt
𝐵𝑎𝑆𝑂4
Grams of BaSO4 by NH4SO4 = X x
𝑁𝐻4𝑆𝑂4
233.38
= X x 132.14
= X 1.7662
𝐵𝑎𝑆𝑂4
Grams of BaSO4 by Mohr’s salt = (0.500 – x) x
𝑀𝑜ℎ𝑟 ′𝑠 𝑆𝑎𝑙𝑡
233.38
= (0.500 – x) x
392.13
= (0.500 – x) 0.5952
1.7662 x + 0.5952 (0.500 –x) = -7500
1.7662 x + 0.2976 -.5952x -=.7500
17662x - .5952x = .7500 – 0.2976
1.171𝑥 0.4524
1.171 = 1.171
x = 0.3863
0.3863
Percentage of NH4SO4 = x 100 = 77.26%
0.500
Percentage of Mohr’s Salt = 100 – 77.26 = 22.74%
4FeSO4 (NH4)2SO4 x 6H2O + 6O2 4Fe2O3 + 8NH4SO4 + 24H2O
4𝐹𝑒2𝑂3 159.64 𝑔
0.2 g x 4𝐹𝑒𝑆𝑂4(𝑁𝐻4)𝑆𝑂46𝐻2𝑂x 1 𝑚𝑜𝑙 𝐹𝑒2𝑂3
= 31.94 g Fe2O3

51. A chloride mixture is prepared by grinding together pure BaCl2∙2H2O, KCl and NaCl. What is the
smallest volume of 0.15 M silver nitrate solution that may be used for complete precipitation of chloride
from
0.3 g sample of the mixture which may contain any or all the constituents above?

0.15=0.3 g/ 170 g/mol × Volume of solution

Volume=0.3 g/ 170 g/mol × 0.15 M


=0.011 Liters
52. What weight of sample should be taken for
analysis so that each 10 mg precipitated AgCl represents 1% Ag 2 O in the original sample?

mass sample Ag2O


%Ag2O= mass sample ×100%

1g 231.735g/mol
massAg2O=10.00mg× x = 0.01617g
1000mg 143.32 g/mol
mass Ag2O 0.01617g
mass sample= ×100= x 100= 808.4g
%Ag2O 1.000

53. What weight of sample should be taken for analysis so that exactly twice the weight in milligrams
of precipitated BaSO4 is the percentage of SO3 in the original sample?
Molar mass of Na2SO4 = 142 g/mol
Molar mass of SO3 = 80 g/mol
% SO3 in Na2SO4 = 142 g/mol80 g/mol×100=56.34%
Amount of barium sulfate precipitated = 56.34/2 = 28.17 mg
Molar mass of BaSO4 = 233.38 g/mol
Number of moles of BaSO4 = 28.17 mg / 233.38 g/mol = 1.21 x 10-4 mol
Number of moles of Na2SO4 = 1.21 x 10-4 mol
Mass of Na2SO4 = 1.21 x 10-4 mol x 142 g/mol = 17.18 mg
54. A 1g sample of a mixture which contains only NaCl and KCl gave a precipitate of AgCl which weighed
2 g. what are the percentages of Na and K in the mixture?
2.000/143.15=0.014
x+y =0.014
x(NaCl) + y (KCl)= 1.000
58.45x+74.55y=1.000
x= 0.014-y
58.45 (0.014-y) +74.55y=1.000
0.8183-58.45y+74.55y=1.000
y= 0.0113
mass of K: 0.0113 x 39.1= 0.042
mol of Na: 0.014-0.0113= 3x10-3
mass of Na: 3x10-3 x 23= 0.069
%Na: 0.069/1.000 x 100= 6.9%
%K: 0.442/1.000 x100=44.2%

55. I- can be separated from other halides by precipitation as PdI2 and weighed as such or reduce in a
current of H2 to Pd. A 0.5000g sample of KI and NaCl and inert impurities gave a precipitate of mixed silver
halides which weighed 0.8000g. A 0.2000g sample yielded 0.0425 g metallic palladium. Find the percentages of
NaCl and KI in the sample.

1 𝑚𝑜𝑙 𝐾𝐼 1 𝑚𝑜𝑙 𝐼 1 𝑚𝑜𝑙 𝑃𝑑𝐼2 1 𝑚𝑜𝑙 𝑃𝑑 106.42𝑔


Mass KI x 166𝑔 x 1𝑚𝑜𝑙 𝐾𝐼x 2𝑚𝑜𝑙 𝐼 x 1 𝑚𝑜𝑙 𝑃𝑑𝐼2
x 1𝑚𝑜𝑙 𝑃𝑑
= 0.04250g
Mass KI in o.2000g sample: 0.1326 grams
0.1326𝐾𝐼
𝑚𝑎𝑠𝑠 𝐾𝐼
= 0.5000𝑔 𝑠𝑎𝑚𝑝𝑙𝑒
0.2000𝑔 𝑠𝑎𝑚𝑝𝑙𝑒
Mass KI in 0.5000g sample= 0.3315 grams
%KI = (0.3315g/0.5000g)*100=66.3%
1 𝑚𝑜𝑙 𝐾𝐼 1 𝑚𝑜𝑙 𝐼 1 𝑚𝑜𝑙 𝐴𝑔𝐼 234.77𝑔 1 𝑚𝑜𝑙 𝑁𝑎𝐶𝑙 1 𝑚𝑜𝑙 𝐶𝑙 1 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙 143.32𝑔
Mass KI x x x x + Mass NaCl x x x x =
0.8000g 166𝑔 1𝑚𝑜𝑙 𝐾𝐼 1𝑚𝑜𝑙 𝐼 1 𝑚𝑜𝑙 𝐴𝑔𝐼 58.44𝑔 1𝑚𝑜𝑙 𝑁𝑎𝐶𝑙 1𝑚𝑜𝑙𝐶𝑙 1 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙

1 𝑚𝑜𝑙 𝐾𝐼 1 𝑚𝑜𝑙 𝐼 1 𝑚𝑜𝑙 𝐴𝑔𝐼 234.77𝑔 1 𝑚𝑜𝑙 𝑁𝑎𝐶𝑙 1 𝑚𝑜𝑙 𝐶𝑙 1 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙 143.32𝑔
0.3315gx 166𝑔
x 1𝑚𝑜𝑙 𝐾𝐼x 1𝑚𝑜𝑙 𝐼x 1 𝑚𝑜𝑙 𝐴𝑔𝐼 + Mass NaCl x 58.44𝑔 x 1𝑚𝑜𝑙 𝑁𝑎𝐶𝑙 x 1𝑚𝑜𝑙𝐶𝑙 x 1 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙
=
0.8000g
Mass of NaCl in 0.5000g sample: 0.1350 grams
%NaCl = (0.1350g/0.5000g)*100=27%

56. A 3.500g portion of a sample containing NaBr and Na 2SO4 is dissolved and diluted to 250 ml. one-fifth
aliquot potions are titrated by silver nitrate, an average of 42.50 ml of solution being required for the aliquot
portion. In standardization 1 ml AgNO3 is found to be equivalent to 0.01250 g KBr. Compute the percentage of
Br in the sample. How many grams of sodium sulfate are present in the sample?
𝐵𝑟 𝐵𝑟
0.01250 𝐾𝐵𝑟 (𝑔 𝑝𝑝𝑡)
𝑁𝑎𝐵𝑟 (𝑁𝑎2𝑆𝑂4) 𝑔
%Br = 3.500 𝑔 𝑠𝑎𝑚𝑝𝑙𝑒 x 100%
79.90
0.01250 ( )
= 244.94
x 100% = 0.12 % Br
3.500

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑁𝑎2𝑆𝑂4 𝑀𝑜𝑙 𝑅𝑎𝑡𝑖𝑜 𝑆𝑂4 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑂4


g SO4 = 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑂4 x 𝑀𝑜𝑙 𝑅𝑎𝑡𝑖𝑜 𝑁𝑎2𝑆𝑂4 X 𝑀𝑜𝑙𝑒𝑠 𝑆𝑂4

142.04 𝑔 1𝑚𝑜𝑙 𝑆𝑂4


g SO4 = x 96.06 = 142.04 g SO4
X
𝑔
96.06 𝑔 1 𝑚𝑜𝑙 𝑁𝑎2𝑆𝑂4 1 𝑚𝑜𝑙𝑒 𝑆𝑂4
57. A mixture of AgCl and AgI is heated in a current of chlorine, thereby converting the AgI to AgCl. This
conversion causes a loss of 6% of the original weight. Find the percentage of Cl in the mixture.

XgAgCl + YgAgI 1.0 g (1-y + 0.611) = 0.94


AgCl = 1 Ag (107.9) + 1Cl (35.5) = 143.4 AgCl -0.389y =0.06
AgI = 1 Ag (107.9) + 1 I (126.9) = 234.8 AgI y = 0.154g AgI
XgAgCl + YgAgI (143.4𝑔 𝐴𝑔𝐶𝑙) = 0.94 x = 0.846 AgCl
234.8 𝑔 𝐴𝑔𝐼
x + y = 1.0 x + 0.611 = 0.94

mol ratio 1:1:1

0.846 𝑔 𝐴𝑔𝐶𝑙 1 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙 1 𝑚𝑜𝑙 𝐶𝑙


( 1𝑔 )(143.4 𝑔 𝐴𝑔𝐶𝑙 )( 1 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙
)
35.5 𝑔 𝐶𝑙
( ) = 0.21 g Cl
1 𝑚𝑜𝑙 𝐶𝑙

% Cl = (0.21) x 100 = 21%


10

58. In what proportions should potassium and ammonium bromides be mixed to make a salt mixture that is
70% Br?
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑒 (𝑁𝐻4𝐵𝑟)
K + NH4Br = KBr +NH3 %(w/w) = x 100
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑒
3K + 3NH4Br =3KBr +4NH3 70% =
411.03 𝑔
70%
𝑀𝑎𝑠𝑠 𝑆𝑜𝑙𝑢𝑡𝑒
100% = 411.03 𝑔
39.10 (70)(411.03𝑔)
3 moles K x = 117.3 g Mass NH4Br =
1 𝑚𝑜𝑙 𝐾 97.91 𝑔 100
3 moles NH4Br x = 293.73 Mass of NH4Br = 287.72 g
1 𝑚𝑜𝑙 NH4Br
Mass Solution = 411.03 g Mass of K = Mass Solution – Mass of NH4Br
= 411.03 g – 287.72 g
Mass of K = 123. 31 g

59. How many grams KCL should be added to 100g NaCl to make a mixture that contains 55% Cl?
𝑔𝐾𝐶𝑙
100 g NaCl
100𝑔 𝑁𝑎𝐶𝑙 x 100 = 55%
55% Cl
𝑔𝐾𝐶𝑙
Formula: x 100 = 0.55
100 𝑔 𝑁𝑎𝐶𝑙
𝑤
x 100 % gKCl = (0.55)(100g NaCl)
𝑤
= 55 g KCl

60. A mixture BaCl2 and KCl contains 40% Cl. What is the percentage of barium in the mixture? How many
grams of BaCl2 should be mixed with 0.5000 g KCl to produce the mixture?

Ba – 137.33g K – 39.10g Ba = 137.33𝑔(1) = 65.95 %


208.23𝑔
35.45𝑔(2)
Cl – 35.45g KCl – 74.55g Cl2 = = 34.05 %
208.23𝑔
39.10𝑔(1)
BaCl2 – 208.23g K= = 52.45 %
74.55𝑔
35.45𝑔(1)
Formula: Cl = = 47.55 %
74.55𝑔
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Cl =
34.05+47.55 = 40.8 %
2 52.45
K= = 26.23 %
2
𝟔𝟓.𝟗𝟓
Ba = = 32.98 %
𝟐

1 𝑚𝑜𝑙 𝐾𝐶𝑙
0.5000 g KCl x 1 𝑚𝑜𝑙 𝐵𝑎𝐶𝑙2 208.23 𝑔 𝐵𝑎𝐶𝑙2
74.55 𝑔 𝐾𝐶𝑙 x 1 𝑚𝑜𝑙 𝐾𝐶𝑙 x 1 𝑚𝑜𝑙 𝐵𝑎𝐶𝑙2 = 1.40 g BaCl2

61. What is the percentage composition of a mixture of KCL and NH4Cl which has the same percentage
of Cl as NaCl? If 0.5000 g of the mixture is strongly ignited, what is the weight of the residue? All the NH4Cl
is vaporized when the sample is ignited.
Cl in NaCl:
35.35/ 58.45= 0.61
m(KCl) + m(NH4Cl)=
0.5000g m(Cl)= 0.5g x0.6g=
0.3g (Cl)= 0.3/35.45= 0.0085
(Cl)= (KCl)+ (NH4Cl)= 0.0085
KCl= x; NH4Cl= 0.0085-x
74.5x +53.5 (0.0085-x)=0.5000
74.5x +0.45475-53.5x= 0.5000
x=.002
m(KCl)= 0.002x74.5= 0.149g

62. A sample of CaCO3 and FeCO3 contains equal portions of each day by weight. Strong ignition produces
CaO and Fe2O3. What is the weight of a 1.000g sample after through ignition?
CaCO3(s) -> CaO+ CO2
4FeCO3(s) -> 2Fe2O3+ 4CO2
1.000/2= 0.5 each
FeCO3: 0.5g/116= 0.004316 mole
Fe2O3 :0.00215 x 160= 0.3446g
CaO3: 0.5/100 = 0.005 mole
CaO: 0.005x56= .28g
0.28g + 0.3446g = 0.6246g
CHAPTER 6

1. How many significant figures are in each of the following numbers:

(a) 410= 2
(b) 410.0= 4
(c) 0.041= 2
(d) 0.04100=4
(e) 0.41 x 10-8 =2

2. Express the results of the following calculations to the proper number of significant figures:
Ans. (a) 1.119; 1.66 x 103
(a) 1.060 + 0.05974 – 0.0013 =1.118
(b) 14.365 + 0.015 + 12.6 =27.0
(c) 101.65 + 1.283 – (3 x 10-5)= 102.93
(d) 2.5 x 101,562=2.5x105
(e) 15.75 x (300 x104) x 0.000035= 1.66x103
29.74 𝑥 400
(f) = 1.5x105
0.080
12.3456 𝑥 20
(g) 0.002 = 1.2x104

3. The factor for the conversion of U.S. gallons into liters is 3.78553.
Ans. (a) 2.08 liters
(a) Express 0.55 gallons as liters.

1 𝑔𝑎𝑙𝑙𝑜𝑛
3.78533𝐿 0.55 𝑔𝑎𝑙𝑙𝑜𝑛
x 𝑥 = 2.08L

(b) Express 11.99 ml as gallons.


1 𝑔𝑎𝑙𝑙𝑜𝑛
-3
x 0.1199𝐿 = 3.17x10
3.78533𝐿 𝑥

4. If the convention of significant figures is properly used, what is the smallest graduation interval on
a thermometer for which a reading of 96.54°C is recorded?

= 96.5 0C (3 significant figures)

5. Express to the proper number of significant figures:


(a) The density of an object whose volume is 13.25 ml and which weighs 62.5013 g.

62.5013 𝑔
Density = 13.25 𝑚𝑙

= 4.717 g/ml

(b) The percentage of silica in a mineral which weighs 1.0065 g and which yields a precipitate of
SiO2 which weighs 0.0142 g.

1.0065 g : 0.0142 g = x : 100


0.0142923 = 100𝑥
100

= 1.43 %

(c) The result of an analysis which calculates to 0.00296457 and which involves in the calculation
a weight of sample of 0.9572 ± 0.0002 g and a volume of standard solution of 56.13 ± 0.08 ml.

0.9572 ± 0.0002 g = 0.9574/0.957 g


56.13 ± 0.08 ml = 56.21/56.05 ml
0.9574𝑔
= 0.01703255648
56.21𝑚𝑙

0.00296457−0.01703255648
% Error: 0.01703255648

= - 82.59%

6. By use of a table of atomic weights express the molecular weights of the following compounds to the
proper number of significant figures to agree with the least precisely known atomic weight involved: (a)
HCl, (b) Au2O3, (c) Eu(NO3)3.

(a) HCl = H – 1.0078


Cl – 35. 446
36. 454 g/mol (5SF)
(b) Au2O3 = Au – 2 x 197.0
O – 3 x 15.999
442 g/mol (4SF)

(c) Eu(NO3)3 = Eu – 1 x 151.96


N – 3 x 14.006
O – 9 x 15.999
337.97 g/mol (5SF)

7. Express the following measurements with the proper number of significant figures to indicate the
highest accuracy obtainable with the instrument used:
Ans. (a) 5.0 g; (d) 0.010000 g; (f) 9.0 ml.
(a) 5 g measured on a laboratory trip scale.

= 5.0 g

(b) 30 g measured on a balance sensitive to 10 mg.

= 30,000 mg

(c) 10 mg weighed on an analytical balance.

= 10.0 g

(d) 10 mg weighed on a microbalance sensitive to 10-6 g.


= 0.010000 g

(e) 9 ml measured in a 100-ml graduated cylinder.

= 9.00 ml

(f) 9 ml measured in a10-ml graduated cylinder.

= 9.0 ml

(g) 9 ml measured from a 50-ml buret.

= 9.0 ml

8. For the results 0.0519, 0.0521, 0.0522, and 0.0520 find:


Ans. (a) 1.9/1000: (b) 2.5/1000; (c) 6/1000; (d) ±0.0002.

GIVEN DEVIATION FROM MEAN, m SQUARE OF DEVIATION


0.0519 -0.0002 4X10-8
0.0521 0.0000 0
0.0522 +0.0001 1X10-8
0.520 -0.0001 1X10-8
TOTAL: 0.2082 TOTAL: 6X10-8

0.2082
MEAN = 4

MEAN = 0.0521

(a) The average deviation in parts per thousand.


0.0004
= 0.001 m
4

𝑚
0.01 0.0521 x 1000

= 1.9/ 1000

(b) The standard deviation in parts per thousand.

Standard Deviation = √6𝑥10−8


4−1
= 1.414213562x10-4

1.41𝑥10−4
= 𝑥1000
0.0521

= 2.7/ 1000

(c) The range in parts per thousand.


0.0522 – 0.0519 = 3x10-4
3𝑥10−4
= 𝑥1000
0.0521
= 6/ 1000

(d) The 95 per cent confidence.

= ±0.0003 x 0.7
= 2.1 x 10-4
= ±0.0002

9. An analyst obtained the following results for the standardization of HCl


solution: 0.1135, 0.1134,0.1136, 0.1144, 0.1132. May any one of these be
discarded?

Ans. Discard 0.1144.


X1 X1 - X (X1 – X )2
0.1135 1.2 x 10-4 1.44 x 10-8
0.1134 -2.2 x 10-4 4.84 x 10-8
0.1136 2 x 10-5 4 x 10-10
0.1144 7.8 x 10-4 6.084 x 10-7
0.1132 -4.2 x 10-4 1.764 x 10-7
X = 0.5681

∑X1
X= 𝑁 = 0.5681 = 0.11362
4

X1 X1 - X (X1 – X )2
0.1135 0.00012 0.0000000144
0.1134 - 0.00022 0. 0000000484
0.1136 0.00002 0. 0000000004
0.1144 0.00078 0.0000006084
0.1132 -0.00042 0.0000001764
X = 0.5681 ∑(X1 – X) 2 = 0.000000878

(0.000000878)2
S=√
5−1

0.000000878
𝑆= 4
S = 0.000000212
UCL X + S = 0.11362 +0.000000212 = 0.1136
LCL X – S = 0.11362 - 0.000000212 = 0.1131

Discard = 0.1144

10. The following results were obtained for the percentage of iron in a sample of pure Fe0: 76.95, 77.02,
76.90, and 77.25.
(a) Compute the standard deviation in parts per thousand.

76.95+77.02+76.90+77.25 ( X1 – X ) (X1 – X )2
X= 4 - 8 x 10-2 6.4 x 10-3
X = 77.03 - 1 x 10-2 1 x 10-4
0.0817 - 1.3 x 10-1 1.69 x 10-2
S = √ 4−1 - 2.2 x 10-1 4.83 x 10-2
S = 1.65 x 10-1 1.65 x 10−1 ∑(X1 – X )2=
S in parts per thousand = 𝑥 1000 = 2.14 8.17x 10-2
77.03
= 2.14/1000

(b) Express the range in parts per thousand.

R = 77.25 – 76.90 = 0.35


Range in parts per thousand = 0.35
77.03 x 1000 = 4.54
= 5.54/1000

(c) What can be said about the presence of systematic errors in these results?

The system error in the result is the imperfect instrument calibration and environmental interference
that causes the inaccuracy of the result in the experiment.

11. Given the results 24.65, 24.78, and 24.55:


(a) Express the range in parts per thousand.

R = 24.78 – 24.55 = 0.23


0.23
R in ppt = 𝑥 1000 = 9.33
24.66
= 9.33/1000

(b) Express the average deviation in parts per thousand.

24.65+24.78+24.55
Mean = 3 = 24.66

Deviation1= |24.66 -24.65| = 0.01


Deviation2 = |24.66 -24.78| = 0.12
Deviation3 = |24.66 -24.55| = 0.11
0.01+0.12+0.11
Average Deviation = 3
= 0.08
Average Deviation in parts per thousand = 0.08 𝑥 1000 = 3.24
24.66
= 3.24/1000

(c) What is the 95 per cent confidence interval?

Range= 0.23
Fc for 95% with N + 3 = 1.3
Confidence Interval = R x Fc = 0.23(1.3) = 0.299
X1
Confidence ( X(95%)
Interval 1 – X ) = ± .299%
(X1 –orX )2
± .3 %
-1 -2
40.02 - 1 x 10 1 x 10
40.12 0
12. May any of the results 40.02, 40.12, 0 40.18 be discarded?
40.16, and
-2
40.16 4 x 10 1.6 x 10-3
0.0152
𝑆=√
-2
40.18 6 x 10 3.6 x 10-3
4 − 1 = 1.31 𝑥 10−1 𝑜𝑟 0.131
X= 40.12 ∑(X1 – X )2=
1.52 x 10-2
UCL X + S = |40.12 + 0.131|= 40.251
LCL X + S = |40.12 - 0.131| = 39.989
Discard: None

13. By how many parts per thousand do the following pairs of results deviate from each
other: (a) 9.5 and 9.7.

Mean = 9.6
Deviation1 = |9.6 - 9.5|=0.1 D eviation1+ Deviation2 0.1+0.1
Deviation2 = |9.6 – 9.7|=0.1 = = 0.1
.1
ppt =
2 2
𝑥 1000 = 10
9.6
10/1000

(b) 0.507 and 0.5012.

Mean = 0.5095
Deviation1 = |0.5095- 0.507|=0.0025 Deviation + Deviation 0.0025+0.0025
1 2
Deviation2 = |0.5095– 0.5012|=0.0025 = = 0.0025
2 2
.0025
ppt = 0.5095 𝑥 1000 = 4.91
4.91/1000

(c) 40.06 and 40.10

Mean = 40.08
Deviation1 = |40.08 - 40.06 |=0.02 D eviation1+ Deviation2 0.02+0.02
Deviation2 = |40.08 – 40.10|=0.02 = = 0.02
.02
ppt =
2 2
40.08 𝑥 1000 = 0.5
0.5/1000

(d) 0.09719 and 0.09717.


Mean = 0.5095
Deviation1 = |0.09718 - 0.09719 |=0.00001 D
1+ D2 0.00001+0.00001
Deviation2 = |0.09718 – 0.09717|=0.00001 = = 0.00001

.00001 2 2
ppt = 0.09719 𝑥 1000 = 0.1
0.1/1000
.
14. The weight of a 10-g sample is known to 1/100,000. How carefully was the sample weighed?
Solution:
1/100,000 = 0.00001
0.00001 ÷ 10 g = .000001
0000001 × 100 % = 0.0001%
15. If a microburet can be read to the nearest 0.001 ml, what total volume should be withdrawn from the
buret so that the volume will be known to a precision of 2/1000?
Ans. 1 ml.

𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑚𝑒𝑎𝑠𝑢𝑟𝑖𝑛𝑔 𝑟𝑎𝑛𝑔𝑒 𝑥 0.001


= 𝑝𝑟𝑒𝑐𝑖𝑠𝑖𝑜𝑛 𝑜𝑓 2/1000
𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑚𝑒𝑎𝑠𝑢𝑟𝑖𝑛𝑔 𝑟𝑎𝑛𝑔𝑒 𝑥 0.001
= 𝑝𝑟𝑒𝑐𝑖𝑠𝑖𝑜𝑛 𝑜𝑓 2/1000
2 𝑚𝑙 (𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑚𝑒𝑎𝑠𝑢𝑟𝑖𝑛𝑔 𝑟𝑎𝑛𝑔𝑒 𝑜𝑓 𝑚𝑖𝑐𝑟𝑜𝑏𝑢𝑟𝑒𝑡) 𝑥 0.001
= 𝑝𝑟𝑒𝑐𝑖𝑠𝑖𝑜𝑛 𝑜𝑓 2/1000
= 1 ml

16. How carefully should a 5-g sample be weighed to achieve a precision of:
(a) 1 per cent, (b) 0.5 per cent, (c) 0.1 per cent?

5 X .01 = 0.05 X 1000 = 50/1000


5 X .005 = 0.025 X 1000 = 25/1000
5 X .001 = 0.005 X 1000 = 5/1000

17. A sample of an alloy is to be analyzed for silver by electrodeposition. If the sample is approximately 20 per
cent Ag, what size sample should be taken for analysis so that the error in determining the weight of the
deposited silver does not exceed 1/1000, provided a balance sensitive to 0.q mg is used?
Ans. 1 g.

Since the weighing is reliable to 0.01 mg and two weighings are required to get the weight of the deposit, the
total error may be as large as 0.02 mg. Since this is to be 1/1000, we have the relation

0.02 mg =
= 0.02 Mg x 1000 = 20 mg
20 mg: X = 20 %: 1000
20000
X = 20
X = 1000 mg or 1 g

18. Copper is to be determined by electrodeposition of the metal form a solution which is approximately 0.5
percent Cu. If the error in determining the weight of the deposited copper is not exceed 1/100 and a balance
which is sensitive to 0.05 mg to be used, what size sample should be taken for analysis? How precisely
should the sample be weighted?

0.10 mg = 1/100
X = 0.10 mg (100)
X = 10 mg (2000)
X = 20,000 mg
X = 20 g
CHAPTER 7
1. Convert to pH values:

a.) [H 3O
 ] = 0.0003 pH = -log (10)
pH = -log ( 3 )
[H O ] pH = -1
[H 3O ]
pH = -log (0.0003) f.)  = 0.50
pH = 0.52 pH = -log ([H O3 ] )
pH = -log (0.50)
[H 3O ] 6
pH = 0.3
 = 18x10
b.) pH = - log ([H O3 ] ) g.) pOH = 8.50
6 pH = 14 - 8.50
pH = - log (18x10
pH = 5.5
pH = 4.74 
[H 3O ] = 0.45x10
9 h.) [OH ]= 0.0000072
] [OH ]
pH = -log ( [H O
3 ) pH pOH = -log (  )
c.)
= -log ( 0.45x109 ) = -log (0.0000072)
pH = 9.35 pOH = 5.14
[H 3O ] pH = 14 - 5.14
 = 1.25
pH = 8.86
3

d.)
  12
pH = -log [H O ]
) i.) [O ]= 10
H
(
pH = -log (1.25) pOH = -log ([OH ] )
pH = - 0.1 12

= -log (10 ) pOH
[H 3O ]
e.) = 10 = 12
pH = -log ( [H O3 ] ) pH = 14 - 12
pH = 2

[H O ]
2. Find the 3
 which corresponds to the following:

a.) pH = 8.95 [H O

3
 ] = 1.41 x 10-4
[H 3O ]
= 108.95 e.) pH = 0.0
[H 3O ] 
 = 1.12 x [H 3O ]
= 100.0
10-9 b.) pH = 12.00 [H 3O ]


=1
[H 3O ]
= 1012 f.) pOH =
[H 3O ]

= 1 x 10-12 4.50
c.) pH = -1 pH = 14 - pOH

[H O ]
= 10
(1) pH = 14 -4.50
pH = 9.5


[H
3
O ] [H3O ]
3
= 10 
= 109.5
[H O ]
3
= 103.85
d.) pH = 3.85
[ O
 ] = 33.16 x 10-10 g.)
H pOH = 15
pH = 14 - pOH
pH = 14 -15 pH = 14 - pOH
pH = -1 pH = 14 -0.30
[H 3O ]

= 10(1) pH = 13.7
[H3O  ] 

= 10 [H 3O ] = 10 13.7
h.) pOH = 0.30 [H O
3  ] = 2.0 x 10-14


3. Find the [OH ] which corresponds to the values in problem 2.

a.) pH = 8.95
[H 3O ] e.) pH = 0.0
 = 
[H 3O ]
1.12x10
9 =1
14 14
[OH  1x10 1x10
]= 9 [OH ]= 

1.12x10 1
 
[OH ]= 8.93 x 10-6 [OH ]= 1 x 10-14
b.) pH = 12.00 f.) pOH = 4.50
 
[H 3O ] = 12 [OH ]= 10 4.50
1x10
14
[OH  1x10 
[OH ]= 3.16 x 10-5
]= 12
1x10 g.) pOH = 15.0
  15
[OH ]= [OH ]= 10
0.01 
[OH ]= 1 x 10-15
c.) pH = -1

h.) pOH = 0.30
[H 3O ]
= 10
14  0.30
[OH  1x10 [OH ]= 10
]= 
10 [OH ]= 2.0 x 10-14

[OH ]= 1 x 10-15
d.) pH = 3.85
[H 3O ] 4
 = 1.41x10
14
[OH  1x10
]= 4
1.41x10

[OH ]= 7.9 x 10-11

4. At 100°C Kw is 5.8 x 10-13. What is the pH pf a neutral solution at 100°C? Ans. 6.12

25℃ Kw = 1.0 x 10-14


-log (5.8 x 10-13)
12.24/2
= 6.12
Acidic
5. At 0°C Kw is 1.2 x 10-15. Is a solution whose pH at 0°C is 7 neutral, acidic or basic?
-log (1.2 x 10-15)
14.42/2
= 7.46
Acidic

6. Calculate the pH of the following solutions:


a) 0.001M HCl

ph= -log( n.factor × molarity ) pH= -log( 1× 0.001) or -log(10^-3)


n.factor is the no. of hydrogen atoms, which is 1 in =3
HCl

b) 0.1M HNO2

Ka= 4.5 X 10-4 pH= -log(6.7 X 10-3 M)

x2 / 0.1-x x2 / 0.1-x = √𝑥2 = √4.5 X 10^ − = 2.17


4
x= 6.7 X 10-3 M

c) 0.01M KNO2 Ans. (b) 2.15

Ka= 4.0 X 10-4 Kw= 1 X 10-14 5x10-7 = x

1x10-14 / 4x10-4 = 2.5x10-11 -log(5x10-7)= 6.30

2.5x10^-11 = x •x / 0.01 14–6.30 = 7.7

2.5 x 10–13 = x • x pH = 7.7

7. Find the pH of the following solutions:


a) 50 ml 0.0001M NaOH. Ans.10
-log(0.0001M)= 4
pH= 14-4
= 10

b) 10 ml 2.0 M HCl

=-log(2.0M/L x 0.01L/1
=-log(.02)
pH= 1.70

c) 100 ml 0.01M Ba(OH)2 (assume complete ionization)

pOH= -log(OH-
pOH= -log(0.02M/L x 0.1L/1
= -log(0.002
= -(-2.70)
pH= 14-2.70
pH= 11.30

d) 75 ml 0.1M KNO3
KNO3 is a salt

solution

e) 100 ml 0.2M sodium benzoate. Ans. 8.73

C6H5COONa NaOB2

C7H5NaO2

NaOB2 Na+(aq) + OB2-(aq)


OB2(aq) + H2O HOB2(aq) + OH- (aq)
- -
OB2 (aq) HOB2(aq) + OH (aq)

I 0.2M 0 0

C + 0.2 - 0.2 - 0.2


E 0 0.2 0.2

[OH-] = 0.2 pOH = 0.70


-log[OH-] = -log (0.2) 14 = pH + 0.70
pH = 14 – 0.70 pH = 13.3

f) 5mM NH4Cl added to 200 ml 0.1M NH3

20 mmols NH4Cl

60 mmols NH3

40 mmols/ 200= 1/5


-log(1/5) = 0.70

g) 0.025 mole KOH in 125 ml of solution

= 0.025 mol/ .125 L pOH= -log(.2M


= .2 M = .70
pH= 14-.70
= 13.30

h) 1 g HOAc in 100 ml

molar mass of HOAc= 60.06 g/mol 50


𝑚𝑜𝑙 𝐻𝑂𝐴𝑐
500 500
3003 𝑀 = 3003 M OH-
mass HOAc= 1g 3003

= 0.1𝐿

volume solution= 1.0X10-14 *use Kw to calculate H+ in the solution

*conversion into molar mass H+= Kw/ OH- = 1.0X10-14/ 500 M= 6.006X10-14 M
3003
1 𝑚𝑜𝑙 𝐻𝑂𝐴𝑐 50
1g HOAc X 60.06 𝑔 𝐻𝑂𝐴𝑐
= 3003 pH= -log(H+= -log(6.006X10-14 M

*molarity pH= 12.22

i) 1 g HCl in 100 ml

1g HCl x 1mol HCl/ 36.46g HCl= 50


1823mol HCl pH= -log( 50 )mol HCl
1823
50
𝑚𝑜𝑙 𝐻𝐶𝑙
1823 500 pH= 0.56
1823
M HCl
= 0.1 𝐿
j) 1 g HCl and 1 g KCl in 100 ml
1 𝑚𝑜𝑙 𝐻𝐶𝑙 0.05 𝑚𝑜𝑙
1 g HCl x 36 𝑔 𝐻𝐶𝑙 = 0.1 𝐿 = 0.5 M
1 𝑚𝑜𝑙 𝐾𝐶𝑙 0.01 𝑚𝑜𝑙
1 g KCl x = = 0.1 M
75 𝑔 𝐾𝐶𝑙 0.1 𝐿

pH = pKa + log (𝐵) pH = - 6.72


𝐴

= -6.24 + log (0.1)


0.3

k) 1 g HOAc and 1 g KOAc in 100 ml Ans. 4.53

1 𝑚𝑜𝑙 𝐻𝑂𝐴𝑐 0.017


1 g HOAc x 60 𝑔 𝐻𝑂𝐴𝑐 = .1𝐿

1 𝑚𝑜𝑙 𝐾𝑂𝐴𝑐 0.010


1 g KOAc x 95 𝑔 𝐾𝑂𝐴𝑐 = .1𝐿

HOAc = 0.17 M = 4.74 + log (0.10)


0.17
KOAc = 0.10 M
pH = 4.51
pH = pKa + log ( ) 𝐵
𝐴

8. 50 ml 0.1M NH3 is mixed with 100 ml 0.1M HCl. What is the pH of the resulting mixture?
Ans. 1.48
NH3 initially= (50mL) (0.1M)= 5mmol
[NH3 ]final = 5/ total mL= 5/150= 3.33x10-2
mmol HCL added= (100mL) (0.1M)= 10 mmol
-log(3.33x10-2)
mmol HCL remaining= (5-10)= 5 mmol
= 1.48

9. Repeat problem 8, but use 0.1M HCl and 100 ml 0.1M NH3.

HCl initially= (100mL) (0.1M)= 10mmol [HCl]final= 5/toal mL= 5/150= 3.33x10-2
mmol NH3 added= (50mL) (0.1M)= 5mmol -log(3.33x10-2)
mmol NH3 remaining= (10-5)= 5 mmol = 1.48

10. How many grams of KOH must be dissolved in 400 ml to produce a solution whose pH is 10.95?

pH = 10.95

pOH = 3.05
[OH-] = 8.91x10^-4 M
Mass of KOH = (8.91x10^-4 mol/L) (56 g/mol)

= 0.049 g/L
Mass req. for 400 ml solution = (0.049 g/L) (0.4 L)

= 0.02g KOH

11. Repeat problem 10, but use NH3 in place of KOH. Ans. 0.30 g NH3

pH = 10.95 NH3 + H20 NH4 + OH-


pOH = 3.05 Kb = [NH4] [OH-]
[OH-] = 8.91x10^-4 M [NH3]
NH3 = 1.77x10^-5 = [8.91x10^-4]^2 / 1.77x10^-5

= 0.04485 M

12. If the solution of problems 10 and 11 are mixed, what is the pH of the mixture?

KOH solution : M = 8.91x10^-4

V = 400 ml M1V1 + M2V2 = M3V3


NH3 solution : M = 8.91x10^-4 M3 = [(8.91x10^-4 mol/L) (400 ml)] +
V = 400 ml [(8.91x10^-4 mol/L) (400 ml)] / 800 ml

V3 = 800 ml M3 = 8.91x10^-4

13. How many milliliters of 0.100M HCl must be diluted to 250. 0 ml to produce a solution of pH 2.50?
Ans. 8.0 ml
pH= 2.50
M1V1 = M2V2
H3O+ = 3.16x10^-3
V1= (3.16x10^-3) (250 ml) / 0.1 M
V1= 8.0 ml

14. How many drops of 0.1M HCl must be added to 100 ml of water to change the pH from 7 to 4? Assume
that a drop is 0.05 ml. Repeat the calculations using 1N acid.

Initial pH = 7 = 1x10^-7
Final pH = 4 = 1x10^-4 V1 = (1x10^-4) (100 ml) / 0.1 M
1M HCl = 1N HCl V1 = 0.1 ml or 2 drops of 0.1 M HCl
M1V1 = M2V2

15. 200 ml 0.001M Na OH is added to 300 ml 0.0005M HCl. What is the pH of the solution?
Ans. 10.0
300 mL (0.0005 mm/mL) = 0.15
200 mL (0.001 mm/mL) = 0.2
pH = -log (0.0001)
500 mL 0.05
=4
0.05
= 0.001 𝑚
500

16. Is it possible at room temperature to prepare a NaOH solution of pH 15?

20-23° C or 68-77 °F – room temperature pH + (-1.89) = 14 >> pH + 1.83 = 14


pH + pOH = 14 pH = 14 + 1.89 pH = 15.83
NaOH; pH = 15 pH = 15.89
pOH = -log (77°F) >> pOH = -log (68) NOT POSSIBLE
= -1.89 = -1.83

17. 10 ml 0.2M HCl is added to 100 ml 0.1M HCl. What is the pH of the mixture? Ans. 0.96

100 mL ( 0.1 mm/ mL ) = 10 8


= 0.073 𝑚
10 mL ( 0.2 mm/mL ) = 2 110
110 mL 8
pH = -log (0.73)
= 1.1
18. 25 ml 0.2M HOAc is diluted to 75 ml and titrated with 0.1M NaOH. Find the pH when half the acid has
been neutralized

75 mL (0.1 mm/mL) = 7.5 mm


12.5 mL (0.2 mm/mL) = 2.5 mm
87.5 5
5
87.5 = 0.057 𝑚
pH = -log (0.057)
= 1.25

19. What color will each of the following indicators have in the solution problem 6? Bromphenol blue,
methyl red, phenol red

a) 0.001M HCl
pH = - log (0.001) = 3 b) 0.1 M HNO2 c) 0. 01 M KNO2
Bromphenol blue pH = -log (0.1) = 1 pH = - log (0.01) = 2
Methyl Red Thymol Blue

20. An indicator which is a weak monobasic acid is blue in a strongly acid solution and yellow in a strongly
basic one. If Kind is 10-10, what color would this indicator have in a solution of pH 7?
Ans. 9.82; blue

In + H2O 𝑶𝑯− + InH+

[𝑶𝑯−][𝑰𝒏𝑯+]
𝑲𝑰𝒏 =
[𝑰𝒏]
𝐾𝐼𝑛 = [𝑂𝐻−] pH = 7
𝐾𝐼𝑛 = 10−10 Blue

21. The Kind for an indicator which is a weak monoacidic base is 10-5. What is the pH when the indicator
is equally divided between its two colored forms?

In + H2O 𝑶𝑯− + InH+

[𝑶𝑯−][𝑰𝒏𝑯+] 𝒑𝑶𝑯 = −𝐥𝐨𝐠(𝑶𝑯−) 𝐩𝐇 = 𝟏𝟒 – 𝐩𝐎𝐇


𝑲𝑰𝒏 = −5
[𝑰𝒏]
𝑝𝑂𝐻 = − log(10 ) pH = 14 − 5
𝐾𝐼𝑛 = [𝑂𝐻−]
𝑝𝑂𝐻 = 5 𝑝𝐻 = 9
𝐾𝐼𝑛 = 10−5

22. What is the concentration of HCl present in solution when methy yellow shows its intermediate color?

pH range of methyl yellow: 2.9-4.0 pH in its intermediate color: 3.45


[𝐻+] = 10−𝑝𝐻 = 10−3.45 = 3.5 × 10−4

𝑯𝑪𝒍 + 𝑯𝟐𝑶 → 𝑯𝟑𝑶 + 𝑪𝒍−


Before x I 0 0
Change −3.5 × 10−4 I +3.5 × 10−4 +3.5 × 10−4
After 𝑥 − 3.5 × 10−4 I 3.5 × 10−4 3.5 × 10−4

𝑲𝒂 = [𝑯𝟑𝑶+][𝑪𝒍−]
[𝑯𝑪𝒍]
−4 2
1.3 × 106 = (3.5 × 10 )
𝑥 − 3.5 × 10−4
−4
(3.5 × 10−4)2
𝑥 − 3.5 × 10
=
1.3 × 106
𝑥 − 3.5 × 10 = 9.42 × 10−14
−4

𝑥 = 9.42 × 10−14 + 3.5 × 10−4


𝑥 = 3.5 × 10−4 𝑀

23. Repeat problem 22, but use HOAc. Ans. Around 8.7 x 10-3M

pH range of methyl yellow: 2.9-4.0 pH in its intermediate color: 3.45


[𝐻+] = 10−𝑝𝐻 = 10−3.45 = 3.5 × 10−4

𝑯𝑪𝒍 + 𝑯𝟐𝑶 → 𝑯𝟑𝑶 + 𝑪𝒍−


Before x I 0 0
Change −3.5 × 10−4 I +3.5 × 10−4 +3.5 × 10−4
After 𝑥 − 3.5 × 10−4 I 3.5 × 10−4 3.5 × 10−4

[𝑯𝟑𝑶+][𝑶𝑨𝒄−]
𝑲𝒂 =
[𝑯𝑶𝑨𝒄]
(3.5 × 10−4)2
1.8 × 10 −5 =
𝑥 − 3.5 × 10−4
(3.5 × 10−4)2
𝑥 − 3.5 × 10 −4 =
1.8 × 10−5
𝑥 − 3.5 × 10−4 = 6.8 × 10−3
𝑥 = 6.8 × 10−3 + 3.5 × 10−4
𝑥 = 7.16 × 10 −3𝑀

24. What is the pH at the equivalence point when 50 ml 0.1M HCl is diluted to 75 ml and titrated with 0.2M
NaOH?
𝑫𝒊𝒍𝒖𝒕𝒊𝒐𝒏 𝒇𝒐𝒓𝒎𝒖𝒍𝒂: 𝑴𝟏𝑽𝟏 = 𝑴𝟐𝑽𝟐
(0.1𝑀 𝐻𝐶𝑙)(0.05𝐿) 𝑀2 (0.075𝐿)
0.75𝐿 = 0.75𝐿
0.067𝑀 = 𝑀2
𝑽𝒆𝒒
(0.067𝑀 𝐻𝐶𝑙)(0.75𝐿) (0.2𝑀 𝑁𝑎𝑂𝐻)𝑉2
0.2𝑀 = 0.2𝑀
0.025𝐿 = 𝑉2
𝑯𝑪𝒍 + 𝑵𝒂𝑶𝑯 → 𝑯𝟐𝑶 + 𝑵𝒂𝑶𝑨𝒄
Before 0.005 0.0025 I 0
Change -0.0025 -0.0025 I +0.0025
After 0.0025 0 I 0.0025

0.067 𝑚𝑜𝑙 × 0.075 𝐿 = 0.005 𝑚𝑜𝑙 𝐻𝐶𝑙


𝐿 1

𝑚𝑜𝑙 0.025𝐿 = 0.0025 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻


0.2 𝐿 × 1

0.0025 𝑚𝑜𝑙
0.125𝐿 = 0.02 𝑀 𝐻𝐶𝑙
*0.125 L is the total volume,
0.050𝐿 + 0.075𝐿 = 0.125𝐿
𝑝𝐻 = −𝑙𝑜𝑔 (0.02)
𝑝𝐻 = 1.69

25. Repeat problem 24, but use HOAc.

𝑫𝒊𝒍𝒖𝒕𝒊𝒐𝒏 𝒇𝒐𝒓𝒎𝒖𝒍𝒂: 𝑴𝟏𝑽𝟏 = 𝑴𝟐𝑽𝟐


(0.1𝑀 𝐻𝑂𝐴𝑐)(0.05𝐿) 𝑀2 (0.075𝐿)
=
0.75𝐿 0.75𝐿
0.067𝑀 = 𝑀2
𝑽𝒆𝒒
(0.067𝑀 𝐻𝑂𝐴𝑐)(0.75𝐿) (0.2 𝑀 𝑁𝑎𝑂𝐻)𝑉2
0.2𝑀 = 0.2𝑀
0.025𝐿 = 𝑉2
𝑯𝑶𝑨𝒄 + 𝑵𝒂𝑶𝑯 → 𝑯𝟐𝑶 + 𝑵𝒂𝑶𝑨𝒄
Before 0.005 0.0025 I 0
Change -0.0025 -0.0025 I +0.0025
After 0.0025 0 I 0.0025

0.067 𝑚𝑜𝑙
𝐿 0.075𝐿 𝒑𝑯 = 𝒑𝑲𝒂 + 𝐥𝐨𝐠(𝒃𝒂𝒔𝒆) 𝑝𝐾𝑎 = 4.74
× 1 = 𝒂𝒄𝒊𝒅
0.005 𝑚𝑜𝑙 𝐻𝑂𝐴𝑐 𝑝𝐻 = 4.74 + log(0.0025 )
𝑝𝐾𝑎 = −𝑙𝑜𝑔 (𝐾𝑎) 0.0025
𝑚𝑜𝑙 0.025𝐿
0.2 × = 1 𝑝𝐾𝑎 = −𝑙𝑜𝑔 (1.8 × 10−5) 𝑝𝐻 = 4.74
0.0025 𝑚𝑜𝑙 𝑁𝑎𝑂𝐻

26. What is the pH at the equivalence point in the titration of 5mM KHP (potassium acid phthalate) dissolved
in 100 ml of water and titrated with 0.1M NaOH? Neglect anything but the first step of the hydrosis.
Ans. 8.96

[KHP]= 5mol  0.5M (0.05M )(100mL)


100m 0.1M  50mL /
0.05L
L

KHC8H4O4 + NaOH KNaC8H4O4 + H2O


B 0.050 0.050 0 0
C -0.050 -0.050 +0.050 +0.050
A 0 0 0.050 0.050

0.05M 0.1L
  0.005M 0.1M 0.005L 0.050 mol

0.005M  = 0.033 𝑀
L 1 L 1 0.15 L

KNaC8H4O4 OH- + KHC8H4O4


I 0.033 0 0
C -x +x +x
E 0.033-x x x

Kp=

14
1.010 9
2.5410
3.910 
6
x2
11
0.033 
2 11 6
x  8.4510 x  9.1910
2.5410

-log[ 9.19106 ]= 5.04


pH=14-5.04

= 8.96

27.0.025 mole Na2CO3 is dissolved in150 ml of water and titrated with 1.0M HCl, using methyl red as the
indicator. Find the approximate pH at the equivalence point.

0.025mol (1.0M )V2


= 0.167 Na2CO (0.167M )(.150L)
M = (1.0M )
3
.150L 1.0M
Veq= 0.025 L

Na2CO3 (aq) + HCl (aq) NaCl (aq) + H2CO3 (aq)


B 0.025 0.025 0 0
C -0.025 - 0.025 +0.025 + 0.025
A 0 0 0.025 0.025

.167mol .150 1mol .025L


 = 0.025 mol Na2CO3  = 0.025 mol HCl
L 1 L 1

H2CO3
0.025mol=
.175L = .143 M

H2CO3 + H2O H3O + HCO3

I .143 0 0
C -x +x +x
E .143-x x x

[x][x]
Ka= 7.151012  x2
.143
6
 2.6710  x
x 
2
11
.143510  .143
 .143  Ph= -log [2.67x106 ]

pH= 5.57

28. Select an indicator for the titration of 50 ml 0.1M benzoic acid (in a volume of 225 ml) by 0.2M KOH.

HC6H5COO (aq) + KOH(aq) → H2O (aq) + KC6H5COO


(aq) B 0.005 0.045 0
C -0.005 -0.005 +0.005
A 0.04 0.005
 0.145M
L 1
.1mol 0.05L
 .275L
0.04mol  0.003mol HC6H5COO [OH-]=
.2mol 0.225L

0.045mol  KOH [C6H5COO]= 0.005mol  0.018M
L 1 .275L

C6H5COO (aq) + H2O (l) HC6H5COO (aq) + OH- (aq)


I .018 0 .145

C -x +x +x
E .018-x x .145+x

[x][.145]
Kb= .018 OH-= .145 + 1.781010

Kb= Kw/Ka OH-= .145


14
110 pOH= -log[.145}
pOH=.84
Kb= 5
7 10
9 [x][.145]
Kb=  1.7810
10
x
1.4310 [.018]

*The indicator to be used is Phenolphthalein because the pH at equivalence point is 9.

(0.1M )(0.05L) (0.2M )V2


0.2M  0.2M

Veq=0.025
L

HC6H5COO (aq)+ KOH (aq) →H2O (l) + KC6H5COO (aq)


B 0.005 0.005 0

C -0.005 -0.005 +0.005


A 0 0 +0.005

C6H5COO= 0.005mol .2mol 0.025L KOH


0.067M  
0.005mol 
0.075L
.1mol 0.05L L 1

0.005mol 
HC6H5COO
L 1

Kb= x2
0.067 6
x 
2
  9.7910
9
0.0671.4310  0.067 pOH= -log[ ]
 0.067 
pOH= 5
9.581106  x2 pH= 14-5
6
9.7910  x pH = 9

29. The acid HA has an ionization constant of 10-5. If 50 ml 0.1N HA is diluted to 200ml and titrated with 0.1N
NaOH:

M1V1  M2V2 0.025M  M2


(0.1M )(0.05L) M 2
(.2L) 
.2L .2L (0.025M )(.2L) (0.1M )V2
0.1M  0.1M
Veq= 0.05L

a) Find the pH before any base is added Ans. 3.30

HA (aq) + H2O(l)→ H3O+(aq) + A-(aq)


B 0.025 0 0
C -x +x +x
A 0.025-x x x

   x2 
Ka= [H 3O ][ A ]
5
0.0251 0.025
0 
[HA]  0.025 

10
5 [x][x]
 0.025
2.5107  x2

4
510  x

pH= -log[ 5104 ]


pH= 3.30

b) Find the pH when 25 ml of base has been added Ans. 5.00


HA (aq) + NaOH(aq)→ H2O(l) + NaA(aq)
B 0.005 0.0025 0
C -0.0025 -0.0025 + 0.0025
A 0.0025 0 0.0025

0.025mol .2L
  0.005mol HA 0.1mol .025L NaOH

0.0025mol 
L 1 L 1

pH= pKa+ log


base
 acid 

pKa= -log[Ka]
pKa=  log 10  5
pH= 5 + log
 .0025 

 
.0025
pKa=5 pH = 5

c) Find the pH at the equivalence point. Ans. 8.65

HA (aq) + NaOH(aq) → H2O(l) + NaA(aq)


B 0.005 0.005 0
C -0.005 -0.005 + 0.005
A 0 0 0.005

0.025mol .2L
  0.005mol HA 0.1mol 0.05L NaOH

0.005mol 
L 1 L 1

A(aq) + H2O (l) HA (aq) + OH- (aq)

I 0.02 0 0
C -x +x +x
E 0.02-x x x


[HA][OH 14 [x][x]
] 110  0.02
Kb=
Kw
A
x 
2
14

Kb b=
= Ka
K
14 0.
0 0  0.02
110 2  0.02 

1
105 
1 21011  x2
6
4.4710  x
9
Kb= 110
pOH= -log [4.47x 10^-6] pH= 14-5.35
pOH= 5.35 pH = 8.65

d) What indicator should be used?

Phenolphthalein

e) Draw the approximate titration curve, using the points which the pH has been computed.

Titration Curve
10
8
6
4
2
0

0 10 20 30 40 50 60

f) Give reasons for thinking that the titration is feasible, without computing the pH at points near the
equivalence point.

The titration is feasible without computing the pH at points near the equivalence point because the solutions
with concentrations that is are by order of 0.1 M and those which ionization constant of the weak acid or base is
10−5 or greater, is known to be feasible.

30. The bas (CH3)3N has an ionization constant of 7 x 10-5. If 50 ml 0.1N (CH3)3N is titrated with 0.1N HCl:
a) Find the pH before any acid is added

(CH3)3N + H2O (CH3)2NH + OH-


I 0.011 0 0
C -x +x +x
E 0.011-x x x

7 
x2 pOH= -log(8.43x 10^-4)
10
5
0.11
x =3.07

7.710 7.710 x 
7 5
pH= 14-3.07
2
x pH = 10.93
4
8.4310  x

b) Find the pH at the equivalence

point M1V1 = M2V2 (CH3)3N HCl

(0.011 𝑚𝑜𝑙) 0.05 𝐿 (0.011 𝑚𝑜𝑙) 0.05 𝐿


(0.011 𝑀)(0.05𝐿) (0.011 𝑀)𝑉2
(0.011 𝑀) = (0.011 𝑀) 𝐿
= 1
= 5.5 x 10-4 𝐿
= 1
= 5.5 x 10-4

V2 = 0.05 L

(CH3)3N(aq) + HCl(aq) (CH3)3NH(aq) + Cl-(aq)

I 5.5 x 10-4 5.5 x 10-4 0

C -5.5 x 10-4 -5.5 x 10-4 +5.5 x 10-4 +5.5 x 10-4

E 0 0 +5.5 x 10-4 5.5 x 10-4


Weak Acid
5.5 𝑥 10 𝑚𝑜𝑙
[(CH ) N H] = −4 = 5.5 x 10-3
3 3
0.1 𝐿

(CH3)3NH + H2O H3O+ + (CH3)3N

I 5.5 x 10-3 M 0 0
C -x +x +x

E 5.5 x 10-3 – x x x

Ka = 𝐾𝑤
𝐾𝑏
=
1 𝑥 10−4 = 1.429 x 10 -10
7 𝑥 10−5

[𝐻3𝑂+ ][(𝐶𝐻3)3𝑁] 8.865 x 10-7 = x


Ka = [(𝐶𝐻3)3𝑁𝐻]
pH = -log (8.87 x 10-7)
1.429 x 10-10 = 𝑥
2
5.5 𝑥 10 −3 pH = 6.05
3 2
7.86 x 10 = x
c) Find the pH when the base two-fifths neutralized
CH3)3N + HCl (CH3)3NH + Cl-
B 5.5 x 10-4 2.2 x 10-4 0 0

C -2.2 x 10-4 -2.2 x 10-4 +2.2 x 10-4 +2.2 x 10-4

A 3.3 x 10-4 2.2 x 10-4 2.2 x 10-4


2
(0.05L) = V2
5 𝐻𝐶𝑙
0.011 𝑚𝑜𝑙 0.02 = 2.2 x 10-4 moles
𝐿 x
0.02 𝐿 = V2 𝐿 1

pH = pKa + log (𝑏𝑎𝑠𝑒)


𝑎𝑐𝑖𝑑

= -log (1.43 x 10-10) + log ( 3 𝑥 10−4 )


2.2 𝑥 10 −4

= 9.84 + 0.176

= 10.02

d) Draw the approximate titration curve

pH 10.93 10.447 10.02 9.67 9.24 6.05 3.95


(ml) Volume 0 10 20 30 40 50 60

Titration Curve
12

10
pH

2
0 10 20 30 40 50 60
Volume in ml
0

Titration Curve

e) What indicator should be used?

Brothymol Blue
pHeq = 6.05

31. Repeat the calculations of problem 29 for the neutralization of 50 ml 0.001N HA by 0.001N NaOH,
assuming an initial volume of 200 ml. Ans. (a) 4.35; (b) 5.00; (c) 7.65
M1V1 = M2V2 (0.001M) (0.05L) = M2 (.2L)
5 𝑥 10−5 𝑀2 (.2𝐿)
= M2V2 = M3V3
(2.5 x 10-4) (.2L) = (.001M) (V3)
5 𝑥 10−5 𝑀2 (.001𝑀)
.2𝐿 .2𝐿 .001𝑀 = .001𝑀

2.5 x 10-4 =
0.05 L = V3
M2
a.)
HA + H2O H3O+ +
A I 2.5 x 10-4 0 0
C -x x x
E 2.5 x 10-4 – x x x

[𝐻3 𝑂+][𝐴−]
Ka = [𝐻𝐴] x2 = 2.5 x 10-9 – 10-5 x pH = -log [5 x 10-5]

10-5 = 𝑥
2 0 = x2 – 2.5 x 10-9 + 10-5 x = 4.30
2.5 𝑥 10 −4
−𝑥
X = 5 x 10-5
b.)
Conversions
0.001 𝑚𝑜𝑙 0.025𝐿
NaOH 𝐿 x 1 = 2.5 x 10-5
2.5 𝑥 10−4𝑚𝑜𝑙 .2𝐿
HA 𝐿 x 1= 5 x 10-5
HA + NaOH H2O + NaA

B 5 x 10-5 2.5 x 10-5

C -2.5 x 10-5 -2.5 x 10-5 +2.5 x 10-5


A 2.5 x 10-5 0 2.5 x 10-5
pH = pKa + log (𝑏𝑎𝑠𝑒) = -log (10-5) + log (2.5 𝑥 10−5)
𝑎𝑐𝑖𝑑 2.5 𝑥 10−5
=5

c.)
0.001 𝑚 0.05𝐿
NaOH 𝐿 x 1 = 5 x 10-5
2.5 𝑥 10−4𝑚𝑜𝑙 .2𝐿
HA 𝐿 x 1= 5 x 10-5
HA + NaOH H2O +NaA

I 5 x 10-5 5 x 10-5 0

C -5 x 10-5 -5 x 10-5 +5 x 10-5


E 0 0 5 x 10-5
5 𝑥 10 𝑚𝑜𝑙
[NaA] = −5 = 2 x 10-4 M
0.25𝐿

Kb = 𝑥 2
𝐵 Kb = 𝐾𝑤
𝐾𝑎
1 x 10-9 = 𝑥
2 1 𝑥 10−14
2 𝑥 10 −4 = = 1 x 10-9
10−5

2 x 10-13 = x2 x = 4.47 x 10-7 pOH = -log (4.47 x 10-7)


= 6.35
pH = 14 – 6.35 = 7.65

d.) Bromothyl Blue

32. Compute pH values and plot on a large scale the titration curve for 0.1N HCl and NaOH.

Theoretical Values: M1V1 = M2V2 2.5 𝑥 10−3 (0.1𝑀)(𝑉2)


0.1 𝑀 = 0.1 𝑀
HCl volume = 25 ml = 0.025 L
(0.1 M)(.025L) = (0.1M)(V2)
Veq = 0.25 L
a.) V = 0
pH = -log [.1M]
=1
1
b.) VNaOH = 10 ml x
1000 𝑚𝑙 = 0.01 M
HCl + NaOH N2O + NaCl

B 2.5 x 10-3 1 x 10-3


C 1 x 10-3 7 x 10-3

A 1.5 x 10-3 0
𝑚𝑜𝑙
[HCl] = 1.5 𝑥 10−3 = 0.043 M pH = -log [0.043 M] = 1.37
0.035𝐿

c.) NaOH .1 x .02 = 2 x 10-3


1.0 𝐿
V = 20 ml x
1000 𝑚𝑙 = 0.020 L
HCl + NaOH H2O + NaCl

B 2.5 x 10-3 2.5x 10-3

C -2.5x 10-3 -2.5x 10-3


A 5 x 10-4 0
5 𝑥 10−4𝑚𝑜𝑙 pH = -log [0.011] = 1.95
[HCl] = = 0.011 M
0.045𝐿

d.) V = 30 ml x 1.0 𝐿
1000 𝑚𝑙 = 0.030 L
NaOH .1 x .03 = 3 x 10-3
HCl + NaOH H2O + NaCl

B 2.5 x 10-3 2.5x 10-3

C -2.5x 10-3 -2.5x 10-3


A 5 x 10-4 0

[NaOH] = 5 𝑥 10−4 = 9.09 x 10-3


0.055

pH = 14 –(-log [9.09 x 10-3])


= 11.96

e.) V = 50 ml x 1.0 𝐿
1000 𝑚𝑙
= 0.050 L
NaOH .1 x .05 = 5 x 10-3
HCl + NaOH H2O + NaCl

B 2.5 x 10-3 5x 10-3

C -2.5x 10-3 -2.5x 10-3


A 0 5 x 10-4
2.5 𝑥 10
[NaOH] = −3 = 0.33
0.075

pOH = -log [0.33]


= 1.477
pH = 14-1.477
= 12.52
Summary of Sample Points
pH 1 1.18 1.37 1.60 1.95 7.00 11.96 12.22 12.36 12.46 12.52
(ml) Volume 0 5 10 15 20 25 30 35 40 45 50
Titration Curve
14

12

10
pH

2
0 5 10 15 20 25 30 35 40 45 50
0 Volume

Titration Curve

33. In a titration 25 ml 0.001N HCl is diluted to 100 ml and titrated by 0.001N NaOH. Compute the pH for the-
addition of 0, 5; 20, 24, 26, 30 ml of base. Plot the results on the same sheet, and compare with the plot of
problem 32.

Conversions:

V1 =
25 𝑚𝑙
x
1𝐿
= 0.025 L M1V1 = M2V2
1 1000 𝑚𝑙
1𝐿
V2 = 1000 𝑚𝑙 x = 0.1 L (0.0001M)(0.025L) = M2 (0.1L)
1000 𝑚𝑙
−5
0.001
M1 = = 0.001 M 2.5 𝑥 10
𝑀2 (0.1𝐿)
0.1 𝐿 x 0.1 𝐿
1
0.001 2.5 x 10-4 M = = HCl
M3 = = 0.001 M
1 M2 M2V2 = M3V3
(2.5 𝑥 10−5)(0.1𝐿) (0.001𝑀)𝑉3
0.001 𝑀 x 0.001 𝑀
0.025 L = V3 = NaOH

a.) base = 0 ml
HCl + H2O H3O+ + Cl

I 2.5 𝑥 10−4

C 2.5 𝑥 10−4 +2.5 𝑥 10−4 +2.5 𝑥 10−4


E 0 2.5 𝑥 10−4 2.5 𝑥 10−4
pH = -log [H3O+] = -log [2.5 𝑥 10−4] = 3.6
b.) base = 5 ml x 1𝐿 1000 𝑚𝑙
= 0.005 L
Conversions:
0.001 𝑀 0.005 𝐿
NaOH 𝐿 x 1 = 5 x 10-6
Total Volume
0.005 + 0.1 = 0.105

HCl + NaOH H 2O + NaCl

B 2.5 𝑥 10−4 5 𝑥 10−6

C −5 𝑥 10−6 −5 𝑥 10−6
A 2 𝑥 10−5 0
2 𝑥 10 𝑚𝑜𝑙𝑒𝑠
[HCl] = −5 = 1.9 x 10-4 M
0.105 𝐿

pH = -log [H3O+]
= -log [1.9 x 10-4]
= 3.72
c.) base = 20 ml x 1𝐿
1000 𝑚𝑙
= 0.020 L
Conversions:
NaOH 0.001 𝑀
x .020 L = 2 x 10-5 mol
𝐿

Total Volume
0.1 + 0.020 = 0.12

HCl + NaOH H 2O + NaCl

B 2.5 𝑥 10−4 2.5 𝑥 10−6

C −2.5 𝑥 10−5 −2.5 𝑥 10−6

A 5 𝑥 10−6 0
5 𝑥 10 𝑚𝑜𝑙𝑒𝑠
[HCl] = −6 = 4.167 x 10-5 M
0.12 𝐿

pH = -log [4.167 x 10-5]


= 4.38
d.) base = 24 ml x 1𝐿
1000 𝑚𝑙
= 0.024 L
Conversions:
0.001 𝑀 0.024𝐿
NaOH x. = 2.4 x 10-5
𝐿 1

Total Volume
0.1 + 0.024 = 0.124L
HCl + NaOH H 2O + NaCl

B 2.5 𝑥 10−5 2.4 𝑥 10−5

C −2.4 𝑥 10−5 −2.4 𝑥 10−5

A 1 𝑥 10−6 0
𝑚𝑜𝑙
[HCl] = 1 𝑥 10−6 = 8.06 x 10-6 M
0.124 𝐿

pH = -log [8.06 x 10-6]


= 5.09

e.) base = 26 ml x 1𝐿
1000 𝑚𝑙
= 0.026 L
Conversions:

NaOH 0.001 𝑀
x . 0.026𝐿 = 2.6 x 10-5
𝐿

Total Volume
0.1 + 0.026 = 0.126L
HCl + NaOH H 2O + NaCl

B 2.5 𝑥 10−5 2.6 𝑥 10−5

C −2.5 𝑥 10−5 −2.5 𝑥 10−5

A 0 1 𝑥 10−6
𝑚𝑜𝑙
[NaOH] = 1 𝑥 10−6 = 7.94 x 10-6 M
0.126 𝐿

pOH = -log [7.94 x 10-6]


= 5.10
pH = 14 – 5.10
= 8.9
f.) base = 30 ml x 1𝐿
1000 𝑚𝑙
= 0.030 L
Conversions:
NaOH 0.001 𝑀
x . 0.030𝐿 = 3 x 10-5
𝐿

Total Volume
0.1 + 0.030 = 0.130L
HCl + NaOH H2 O + NaCl

B 2.5 𝑥 10−5 3 𝑥 10−5

C −2.5 𝑥 10−5 −2.5 𝑥 10−5

A 0 5 𝑥 10−6
𝑚𝑜𝑙
[NaOH] = 5 𝑥 10−6 = 3.85 x 10-5 M
0.130 𝐿

pOH = -log [3.85 x 10-5]


= 4.41
pH = 14 – 4.41
= 9.59
Summary of Sample Points:
pH 3.6 3.72 4.38 5.09 8.9 9.59
(ml) Volume 0 0.005 0.02 0.024 0.026 0.030

Titration Curve
12

10

8
pH

0
0 0.005 0.02 0.024 0.026 0.03
Volume

Titration Curve

34. 50 ml 0.1M HX (Ki = 10-7) is diluted to 75 ml and titrated with 0.2M KOH
a) What color will the indicator methyl red exhibit when enough base has been added to neutralize half the
acid present?
Yellow

b) Select an indicator for the


titration Thmolphthalein
c) Draw the approximate titration curve, and discuss the feasibility of the titration.
Ans. (a) Yellow; (b) thmolphthalein
1
Conversions = V1 = 50 ml x
1000 𝑚𝑙 = .05 L
1
V2 = 75 ml x
1000 𝑚𝑙 = .075 L
M1V1 = M2V2
M2V2 = M3V3 (0.0667M)
(0.1M)(0.05L) = M2(0.075L)
(0.075L) = (0.2M)(V3)
0.0667M = M2
5 𝑥 10−3 𝑉3 (0.2𝑀)
0.2𝑀 x 0.2𝑀

0.025 L = V3
Conversions:
0.0667 𝑚𝑜𝑙 0.075 = 5 x 10-3 moles
HX = 𝐿 x 1
0.2 𝑚𝑜𝑙 0.025
KOH = x = 5 x 10-3 moles
𝐿 1

Total Volume = 0.025 L + 0.075 L = 0.1 L


HX + KOH H2O + KX

B 5 𝑥 10−3 5 𝑥 10−3 0 0
C −5 𝑥 10−3 −5 𝑥 10−3 + 5 𝑥 10−3
A 0 0 5 𝑥 10−3
[5 𝑥 10 ]𝑚𝑜𝑙
[KX] = −3 = 0.5 M Kb = 𝑥2 x = ± 7.07 x 10-5
0.1𝐿
𝐵−𝑥
Kb = 𝐾𝑤 pOH = -log (7.07 x 10-5)
𝐾𝑎 10-7 = 𝑥
2
0.05 𝑀 −𝑥
= 4.15
[1 𝑥 10−4] -9 -7 2
= 10−7 = 1 x 10 -7 5 x 10 – 10 x = x
pH = 14 - 4.15
2 -7 -9
0 = x + 10 x – 5 x 10
= 9.85
a.) V = 0
HX + H2O H3O+ + X
I 0.0667 0 0
C –x +x +x
E 0.0667 – x x x

Ka = 𝑥
2 x = 8.16 x 10-5
𝐻𝐴−𝑥 10-7 = 𝑥
2
0.0667−𝑥
pH = 4.08
6.667 x 10-9 = x2
b.) V = 0.005
KOH = .005 x .2 = 1 x 10-3
HX = 5 x 10-3
HX + KOH H2O + KX
B 5 x 10-3 1 x 10-3 0
C -1 x 10-3 -1 x 10-3 +1 x 10-3
A 4 x 10-3 0 1 x 10-3

pH = pKa + log (1 𝑥 10−3 )


4 𝑥 10 −3

= 7 + (-0.602)
= 6.4
c.) V = 0.01
KOH = .01 x .2 = 2 x 10-3
HX = 5 x 10-3
HX + KOH H2O +

KX B 5 x 10-3 2

x 10-3 0
C -2 x 10-3 -2 x 10-3 +2 x 10-3
A 3 x 10-3 0 +2 x 10-3

pH = pKa + log (2 𝑥 10−3 )


3 𝑥 10 −3

= 7 + (-0.176)
= 6.82
d.) V = 0.015
KOH = .2 x 0.015= 3 x 10-3
HX + KOH H2O + KX
B 5 x 10-3 3 x 10-3 0
C -3 x 10-3 -3 x 10-3 3 x 10-3
A 2 x 10-3 0 3 x 10-3

pH = 7 + log (3 𝑥 10−3 )
2 𝑥 10−3

= 7 + (-0.176)
= 7.18
e.) V = 0.020
KOH = .2 x 0.020= 4 x 10-3
HX + KOH H2O + KX

B 5 x 10-3 -4 x 10-3 0
C -4 x 10-3 -4 x 10-3 4 x 10-3
A 1 x 10-3 0 4 x 10-3

pH = 7 + log (4 𝑥 10−3 )
1 𝑥 10−3

= 7 + .602
= 7.6
f.) V = 0.030
KOH = .2 x 0.030= 6 x 10-3
HX + KOH H2O +

KX B 5 x 10-3 6

x 10-3 0
C -5 x 10-3 -5 x 10-3 +5 x 10-3
A 0 1 x 10-3 5 x 10-3

[KOH] = (1 𝑥 10−3) = 9.5 x 10-3


.105

pOH = -log[9.5 x 10-3]


= 2.02
pH =14 – 2.02
= 11.97
Summary of Sample Points
pH 4.08 6.4 6.82 7.18 7.6 9.84 11.97
(ml) Volume 0 0.005 0.01 0.015 0.020 0.025 0.030

Titration Curve
0.035
0.03
pH

0.025
0.02
0.015
0.01
0.005
0

4.08 6.4 6.82 7.18 7.6 9.84 11.97


Volume

Titration Curve
35. A 0.05M solution of salt C6H5NH3Cl has a pH of 3.00. What is the ionization constant of C6N5NH2?

x = 10 – 3.00 (1 𝑥 10−3)
2
Ka
= 1 x 10-3 =
0.05𝑀

pH = 2 x 10-5

36. It is found that 50.00 ml a carbonate-free base is neutralized to the phenolphthalein end point by 50.00 ml
0.1000N HCl.
a) What volume of HCl is needed to neutralize 50.00 ml of the base to the methyl orange end point, pH 3.80?

Ka = 1.3 x 106 pKa = -log(1.3 x 106)


𝐴−
pH = pKa + log[ ] = - 6.3
𝐻
𝐴
𝐴−
50 ml = 𝐻𝐴 ∙ 103.80−(−6.3)
pH - pKa = log[ ]
𝐻𝐴

10pH-pKa = 𝐴− 50 𝑚𝑙 = 𝐻𝐴 ∙ 1010.1
∙ 𝐻𝐴
𝐻
𝐴 50 𝑚𝑙 𝐻𝐴∙1.26×1010
=
10
1.26×10 1.26×1010

HA =
𝐴− = 𝐻𝐴 ∙ 10𝑝𝐻−𝑝𝐾𝑎 3.97ml

b) What is the normality of the base solution when used with phenolphthalein indicator?

𝑝𝐻 ∙ 3.8 = 3.8𝑝𝐻
𝐻𝐶𝑙 = 5𝑚𝑙2𝑁𝐻𝐶
50𝑚𝑙 ∙ (0.1𝑁 𝐻𝐶𝑙) = 5𝑚𝑙2𝑁𝐻𝐶
50𝑚𝑙 = 5𝑚𝑙2𝑁𝐻𝐶

c) What is the normality of the base solution when used with methyl orange indicator without an
indicator blank, assuming an end pont at pH 3.80? Ans, c) 0.1003N.

𝐴− = 𝐻𝐴 ∙ 10𝑝𝐻−𝑝𝐾𝑎 𝐴− = .1000𝑁 × 1010.1

𝐴− = .1000𝑁 × 103.8−(−6.3) 𝐴− = .1003𝑁

37. An acid HA has an ionization constant of 5 x 10-6. If 50 ml of a 0.1M solution of the acid is diluted to
200 ml and titrated with 0.1N NaOH:
a) Compute the pH when 49.95 ml of base has been added
n = (.025)(.250ml) n = (.1)(.4995ml)
= 6.25 x 10-3mol HA = 4.995 x 10-2 NaOH

𝐻𝐴 + 𝑁𝑎𝑂𝐻 → 𝑁𝑎𝐴 + 𝐻20


B 6.25 x 10-3 4.995 x 10-3 0
C -4.995 x 10-3 -4.995 x 10-3 +4.995 x 10-3
A 1.255 x 10-3 0 +4.995 x 10-3

Ka = 5 x 10-6
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 ⌊ 𝐴−
𝐻𝐴⌋

pKa = -log(Ka) pH = 5.30 + log(4.995 × 10−3)


1.255 × 10 −3

= 5.30 = 5.89

b) Compute the pH when 50.05 ml of base has been added

n = (.025)(.250ml) n = (.1)(.05005ml)
= 6.25 x 10-3mol HA = 5.005 x 10-3mol NaOH

𝐻𝐴 + 𝑁𝑎𝑂𝐻 → 𝑁𝑎𝐴 + 𝐻2𝑂


B 6.25 x 10-3 5.005 x 10-3 0
C -5.005 x 10-3 -5.005 x 10-3 -5.005 x 10-3
A 1.245 x 10-3 0 5.005 x 10-3

Ka = 5 x 10-3
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 ⌊ 𝐴−
𝐻𝐴⌋

pKa = -log(5 x 10-3) pH = 5.30 + log(5.005 ×10−3)


1.245 ×10 −3

= 5.30 pH = 5.90

38. a) How many grams of NaOAc must be added to 300 ml 0.01M HOAc to produce a buffer of pH 6.50?

𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 ⌊
𝐴− ⌋ Ka of HOAc (acetic acid) = 1.8 × 10−5
𝐻𝐴

𝑝𝐻 − 𝑝𝐾𝑎 = 𝑙𝑜𝑔 ⌊𝐴− ⌋ pKa = −𝑙𝑜𝑔 (1.8 × 10−5)


𝐻𝐴
10𝑝𝐻−𝑝𝐾𝑎 = 𝐴− ∙ 𝐻𝐴 pKa = 4.74
𝐻𝐴

[𝐴−] = ⌊𝐻𝐴⌋ ∙ 10𝑝𝐻−𝑝𝐾𝑎

[𝐴−] = 0.01 × 106.50−4.74 𝐶2 = 12 × 2 = 24

= 0.01 × 101.76 𝐻3 = 1 × 3 = 3
[𝐴−] = 0.58 𝑁𝑎 = 23
𝑂2 = 16 × 2 = 32
82𝑔

.58 𝑚𝑜𝑙 𝑁𝑎𝑂𝐴𝑐 .3𝐿 82𝑔 𝑁𝑎𝑂𝐴𝑐


= × × = 14.27𝑔𝑁𝑎𝑂𝐴𝑐
𝐿 1 1𝑚𝑜𝑙 𝑁𝑎𝑂𝐴𝑐

b) 2.00 mM NaOH is added to the buffer above. What is the pH after the addition of the base?

2.00mM = 0.002mol
OH- + HOAc → OAc- + H O
2

B 0.002 3 x 10-3 0.174


C -0.002 -0.002 +0.002
A 0 1 x 10-3 0.176

0.01𝑚𝑜𝑙 𝐻𝑂𝐴𝑐 . 3𝐿
𝐻𝑂𝐴𝑐 = 𝐿 × 1 = 3 × 10−3
. 58𝑚𝑜𝑙 𝑁𝑎𝑂𝐴𝑐 . 3𝐿
𝑁𝑎𝑂𝐴𝑐 = 𝐿 × 1 = 0.174

𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 ⌊
𝐴−
𝐻𝐴 ⌋

= 4.74 + 𝑙𝑜𝑔 ⌊ 0.176 −3



1×10

𝑝𝐻 = 6.99 𝑜𝑟 7

c) What would happen to the buffer if 2.00 mM NaOH additional were introduced?
Ans. a) 14 g; b) 7; c) pH becomes 11.53

𝐴−
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 ⌊ ⌋
𝐻𝐴
𝐴−
𝑝𝐻 − 𝑝𝐾𝑎 = 𝑙𝑜𝑔 ⌊ ⌋
𝐻𝐴
𝐴−
10𝑝𝐻−𝑝𝐾𝑎 = 𝐻𝐴∙ 𝐻𝐴

[𝐴−] = ⌊𝐻𝐴⌋ ∙ 10𝑝𝐻−𝑝𝐾𝑎

[𝐴−] = 3 × 10−3 × 1011.53−4.74

= 3 × 10−3 × 106.79
[𝐴−] = 18497.85

𝑂𝐻− + 𝐻𝑂𝐴𝑐 → 𝑂𝐴𝑐− + 𝐻2𝑂


B 0.002 9 x 10-4 5549.355
C -0.002 -0.002 +0.002
A 0 -1.1 x 10-3 5549.357

3×10−3𝑚𝑜𝑙 𝐻𝑂𝐴𝑐 .3𝐿


𝐿 × 1= 9 × 10−4
18497.85𝑚𝑜𝑙 𝑁𝑎𝑂𝐴𝑐 .3𝐿
𝐿 × 1= 5549.355

pH = 4.74 + 𝑙𝑜𝑔 [ 5549.357−3]


1.1×10

= 11.44
pH becomes 11.44

39. 10 ml 0.1M HCl is added to 100 ml of a solution which is 0.1M bothe in HOAc and NaOAc. By how
many units does the pH change because of the HCl addition?

10 ml .1M HCl = 1mmol HCl


100 ml .1M HOAc = 10mmol HOAc
100 ml .1M NaOAc = 10mmol NaOAc

Ka = 1.8 x 10-5
𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 ⌊ 𝐴−
𝐻𝐴⌋

pKa = -log(Ka) 𝑝𝐻 = 4.74 + 𝑙𝑜𝑔 ⌊10⌋


10

= 4.74 = 4.74

pH HCl = 10-0.1
= 0.79 4.74 + .79 = 5.53
10 units
40. What is the pH of a solution which produces a slight greenish color when bromthymol blue is added as an
indicator? What must be the ratio of [OAc-]/[HOAc] to produce a solution of this pH?
pH=6.4 pKa = -log(Ka)
Ka=1.8 x 10-5 = -log(1.8 x 10-5)
= 4.74

𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 ⌊ 𝐴− ⌋ =101.66


𝐻𝐴
= 45.71
𝑝𝐻 − 𝑝𝐾𝑎 = 𝑙𝑜𝑔 ⌊ 𝐴−
𝐻𝐴 ⌋
𝐴−
10𝑝𝐻−𝑝𝐾𝑎 =
𝐻𝐴 pH = 6.4
= 10pH-pKa ratio = 1 : 45.71

= 106.4 - 4.74

41. Find the pH of a buffer made by dissolving 3 mM NaCN and 5 mM HCN in 250 ml of solution.

5mM HCN, 3mM NaCN & 250 mL


Unknown: pH HCN + H2O ⇌ CN- + H3O+
5mM HCN – 0.005 M KaHCN = 6.2 x 10-10
3mM NaCN – 0.003 M pkaHCN = -log(ka) = 9.21
250 mL – 0.250 mL pH = pka + log ([Base]/[Acid])
NaCN (base) = (0.003 mol / 1L) 0.250L = 7.5 x 10-4 = 9.21+ log ([7.5 x 10-4 mol]/[2.25 x10-3mol])
mol = 9.21+ (-0.222)
HCN (acid) = (0.005 mol / 1L) 0.250L = 1.25 x 10-3
mol = 8.988

42. What is the pH of a buffer which has been prepared by mixing 250 mg NH4Cl and 200 ml 0.1M NH3
solution? What is the pH of this after 10 mM HCl has been added? The addition of the acid dilutes the
mixture to 250 ml. Ans. a) 9.85; b) 9.09

a. 250 mg NH4Cl, 0.1M NH3 & 200mL


Unknown: pH Unknown: pH after the addition of HCl
NH3 (base) = 200 mL (1L/ 1000 mL) (0.1 mol / 1L) = 10mM(1M/ 1000 mM)= 0.010 M
0.02 mol 250 mL – 200 mL (initial volume)
NH4Cl(acid) = 250 mg (1g/ 1000 mg) (1 mol / 53.49g) =50 mL HCl (1L/ 1000 mL) = 0.050 L HCl
= 4.67 x 10-3 mol HCl = (0.010 mol / 1 L) (0.050L) = 5 x 10-4
NH4 + H2O ⇌ NH3 + H3O+ mol NH3 = 0.02 mol
KaNH4 = 5.8 x 10-10 NH4Cl = 4.67 x 10-3 mol
pkaNH4 = -log(5.8 x 10-10) = 9.2366
pH = pka + log ([Base]/[Acid]) Before 0.02 mol 5 x 10-4 mol 4.67 x 10-3 mol
= 9.2366+ log ([0.02mol]/[4.67 x10-3mol]) Change - 5 x 10-4 - 5 x 10-4 + 5 x 10-4
= 9.868 After 0.0195 0 5.17 x 10-
b. Addition of 10mM Hcl, dilution to 250 mL Final volume = initial volume + added volume
= 200 mL + 50 mL = 250 mL (1L/ 1000 mL) = 0.0250L
MNH3 (base) = (0.0195 mol / 0.250 L) = 0.078 M pkaNH4 = -log(5.8 x 10-10) = 9.2366
MNH4(acid) = (5.17 x 10-3 mol / 0.250 L) = 0.02068 M pH = pka + log ([Base]/[Acid])
KaNH4 = 5.8 x 10-10 = 9.2366+ log ([0.078M]/[0.02068M])
= 9.81

43. What is the pH of a buffer made by mixing 43.00 ml 0.1000N NaOH with 50.00 ml 0.100M KHP and
diluting to a volume of 100 ml?

43 mL of 0.1000N NaOH, 50 mL of 0.1000M KHP


& dilution to 100mL solution
Total volume = initial volume + added volume
Unknown: pH
= 93 mL + 100 mL = 193 mL (1L/ 1000
0.1000 N NaOH/1 = M x 1 replaceable ion / 1 –> mL) = 0.193L
M= 0.1000 M
MNaKP (base) = ( 4.3 x 10-3 / 0.193L) = 0.0223 M
NaOH (base) = 43 mL (1L/ 1000 mL) (0.1 mol /
1L) = 4.3 x 10-3 mol MKHP(acid) = (7 x 10-4 mol / 0.193L) = 3.63 x
10-3 M
KHP(acid) = 50 mL (1L/ 1000 mL) (0.1 mol / 1L) =
5 x 10-3 mol KaKHP = 3.91 x 10-6

NaOH + KHP ⇌ H2O + NaKP pkaKHP = -log(3.91 x 10-6) = 5.408

I 4.3 x 10-3 5 x 10-3 0 pH = pka + log ([Base]/[Acid])

C - 4.3 x 10-3 -4.3 x 10-3 +4.3 x 10-3 = 5.408+ log ([0.0223 M]/[3.63 x 10-3 M])

E 0 7 x 10-4 4.3 x 10-3 = 6.19

44. Estimate the pH of a buffer made by adding 10 g NaHCO3 to 250 ml of a solution which is saturated with
Co2 (0.032M). Ans. 7.57

10g NaHCO3, 0.032M H2CO3 & 250 mL


H2O + CO2 –> H2CO3 H2O + CO2 –> H2CO3
Assume: Saturation of CO2 to the solution will react H2CO3 <–> H+ + HCO3-
to produce Carbonic Acid H2CO3- + Na <–> NaHCO3
Unknown: pH
10g NaHCO3 (1mol/ 84.007g)= 0.12 mol NaHCO3 KaH2CO3 = 4.2 x 10-7
250 mL(1L/ 1000 mL) = 0.250 L pka = 6.38
NaHCO3 (base) = 0.12 mol / 250L) = 0.48M pH = pka + log ([Base]/[Acid])
H2CO3(acid) = 0.032 M = 6.38 + 1.18
= 7.55

45. Estimate the pH of a buffer made by mixing 50 ml 0.1 M KH2PO4 with 25 ml 0.1M naOH and diluting 200
ml.
50mL of 0.1M KH2 PO4 & 25mL of 0.1M NaOH 50 mL –> 0.050L
diluted to 200mL solution
25 mL –> 0.025L
Unknown: pH
NaOH (base) = (0.1 mol / 1L) 0.025L = 2.5 x 10-3
mol (limiting reactant) Final volume = initial volume + added volume
KH2PO4 (base) = (0.1 mol / 1L) 0.050L = 5 x 10-3 = 75 mL + 200 mL = 275 mL (1L/ 1000
mol mL) = 0.275L
KH2PO4 + 2NaOH <–> Na2HPO4 + KOH + H2O MKH2PO4 (base) = ( 2.5 x 10-3 mol/ 0.275L) =
I 5 x 10-3 2.5 x 10-3 0 9.09 x 10-3 M
MNaHPO4(acid) = ( 2.5 x 10-3 mol/ 0.275L) = 9.09
C -2.5 x 10-3 -2.5 x 10-3 +2.5 x 10-3
x 10-3 M
E -2.5 x 10-3 0 +2.5 x 10-3
KaKH2PO4 = 1.38 x 10-7
pka =6.86
pH = pka + log ([Base]/[Acid])
= 6.86+ log ([9.09 x 10-3 M]/[9.09 x 10-3 M])
= 6.86
CHAPTER 8:

1. From the solubility-product values in the Appendix, find the solubility expressed in millimoles per milliliter
and in grams per 100 ml for:
(a) PbI2

PbI2; Ksp = 8.4×10-9


PbI2 (s) ↔ Pb2+ (aq) + 2 I ‾ (aq)

I 0 0
C +1x +2x
E X x

Ksp = [Pb+2] [I ‾] 2
Ksp = (x) (2x) 2
8.4×10 -9 = (x) (4x2)
8.4 × 10−9 4𝑥3
= 4
4 -9)1/3 = (x3)1/3
(2.1×10
x = 1.281×10-3 g/L

(b) Hg2Cl2

Hg2Cl2; Ksp = 1×10-18


Hg2Cl2 (s) ↔ 2 Hg2+ (aq) + 2 Cl‾ (aq)

I 0 0
C +2x +2x
E 2x 2x

Ksp = [Hg2+] 2 [Cl-] 2


Ksp = (2x) 2 (2x) 2
1×10-18 = (4x2) (4x2)
1 × 10−18 = 16𝑥4
16 16
(6.25×10-20)1/4 = (x4)1/4
x = 1.581×10-5 g/L

(c) MgCO3

(d) MgCO3; Ksp = 6.8×10-6


MgCO3 (s) = Mg2+ (aq) + CO 32- (aq)

I 0 0
C +1x +1x
E x x

Ksp = [Mg2+] [CO32-]


Ksp = (x) (x)
(6.8×10-6)1/2 = (x2)1/2
x = 2.607×10-3 g/L

2. How many milligrams if PbSO4 will dissolve in 300 ml H2O?

Ans. 9.1 mg.


2-
PbSO4 → Pb2+ + SO4 ; 10-8
Ksp = [Pb2+] [SO42-]
10-8 = [x] 2; x = Pb2+
x = 10-4 M
PbSO4:
Pb2+
1:1
PbSO4 = 10-4 M
mg of PbSO 10−4𝑚𝑜𝑙 303.27 𝑔 1000 𝑚𝑔
4 = × × × 0.3 𝐿 = 9.098 𝑚𝑔
𝐿 𝑚𝑜𝑙 𝑔

3. Find the number of milligrams of AgCl which are left unprecipitated in 200 ml of solution in which the
excess concentration of Ag+ is 10-2 M.
Ans. 2.8 x 10-4 mg.
V = 200 mL/0.2 L
Excess = Ag+ = 10-2 M
AgCl → Ag+ + Cl-
Ksp = [Ag+] [Cl-]
10-10 = [(10-2) + Ag+] [Ag+]
10-10 = [10-2 + x] [x]
x = 10×10-9
AgCl & Ag+ = 1:1 𝑚𝑜𝑙
mg AgCl = 10 × 10−9 × 143.32 𝑔 × 1000 𝑚𝑔 × 0.2 𝐿 = 2.87 × 10−4 𝑚𝑔
𝐿 𝑚𝑜𝑙 𝑔

4. A precipitate of CaC2O4 is digested in a volume of 300 ml. Calculate the percentage loss (in terms of a
theoretical weight of precipitate of 0.2500 g) caused by solubility in the precipitating solution if:
(a) No excess precipitant had been added.

CaC2O4 Ksp = 2.7 x 10-9 S2


𝑚𝑜𝑙 6.142 𝑥 10−5 𝑔 𝐶𝑎𝐶2𝑂4 1.8426 𝑥 10−3
S = 4.7958 x 10-5 𝐿 = 𝐿 = 100 𝑚𝑙
8.426 𝑥 10 𝑔
% loss = −3 x 100 = 0.7370%
0.2500 𝑔

(b) The supernatant liquid contains an excess of 5.0 ml 0.10 M (NH4)2C2O4.

Solubility of CaC2O4=0.67mg/L
CaC2O4 Ca2+ C2O4-2
I Solid 0 1.64E-3 M
C Solid +x +x
E Solid x 1.64E-3 M+x

Ksp=2.3E-9=[x][1.64E-3
M+x] [x]=1.4E-6
M=[CaC2O4]
1.4E − 6 𝑚𝑜𝑙 𝐶𝑎𝐶2𝑂4 120𝑔 𝐶𝑎𝐶2𝑂4
305𝑚𝐿 ∙ 1000𝑚𝐿 𝑠𝑜𝑙𝑛 ∙ 1𝑚𝑜𝑙 𝐶𝑎𝐶2𝑂4 = 5.12𝐸 − 5𝑔
5.12E − 5 𝑔
× 100% = 0.0205%
. 25𝑔

5. The solubility of Ag2CrO4 is 2 x 10-5 mole per 100 ml.


(a) If the possibility of supersaturation is neglected, what is the minimum volume of water required to
dissolve 0.5 mg Ag2CrO4?

Ag CrO
2×10−5 𝑚𝑜𝑙 2×10−5 𝑚𝑜𝑙
2 = 100 𝑚𝑙 =
4
0.1 𝐿
= 2 × 10−4 𝑀
1𝑔
0.5 mg Ag2CrO4 × 𝑚𝑜𝑙 ×
𝐿
× 1000 𝑚𝑙 = 7.54 𝑚𝑙
1000 𝑚𝑔 × 831.73 𝑔 2×10−4 𝑚𝑜𝑙 𝐿

(b) How many milligrams of Ag2CrO4 remain unprecipitated in 200 ml of solution in which there is a
stoichiometric excess of 1.00 Mm CrO4-2 ?
Ans. (a) 7.5 ml; (b) 2.6 mg.
S(Ag2CrO4)2 = 2.5 x 10-5 mole/100 mL
Ksp = [Ag+] [CrO42-]
[Ag+] =2S = 2 x 2 x 10-5 mole/100 mL = 4 x 10-4 mol/L
[CrO42-] = S = 2 x 10-5 mole/100 mL = 2 x 10-4 mol/L
Ksp = (4 x 10-4)2 (2 x 10-4) = 3.2 x 10-11
[Ag+] = 2X
[CrO42-] = 1.00 mM + X = 0.001 M + X
Ksp = [Ag+2] [CrO4 2-]
3.2 x 10-11 = (2X)2 (0.001 + X) = 4X2 (0.001 +X)
4X3 + 0.004X2 – 3.2 x 10-11 = 0
X = 8.58 x 10-5 M
S’ = 8.58 x 10-5 M/2 = 4.29 x 10-5 M
In a 200 mL solution,
n(Ag2CrO4) = 4.29 x 10-5 M x 0.200 L = 8.58 x 10-6 mol
Mw(Ag2CrO4) = 331.73 g/mol
m(Ag2CrO4) = 8.58 x 10-6 mol x 331.73 g/mol = 2.85 x 10-3 g/ 2.85 mg

6. The precipitate AB2 (mol. wt. = 100) is soluble to the extent of 10-4 moles per liter.
(a) How many milligrams of AB2 remain unprecipitated in 250 ml of solution in which the concentration of
excess A+2 ion is 0.0001 M?

AB2 = 100 mol wt. Sol = 250 ml


Ksp = 10-4 moles/liter A+2 = 0.0001 M

AB2 (s) A+2 (aq ) + 2B- (aq)


I 0.0001 M
0
C +x +2x
E 0.0001 + x 2x

Ksp = (A+2) (2B)2


X = 7.07x10-5 M
10-4 moles/liter = (0.0001 + x) (2x2)
10-4 = (0.0001) (2x2) Ksp = (7.07x10-5) (2(7.07x10-5)2
10-4 = (2x10-4) (x2) = 7.07x10-1
X = √10-4 / 2x10-4

7.07 𝑥 10 𝑚𝑜𝑙𝑒𝑠
−13 x 0.25 L = 1.77x10-13 moles
𝐿

1.77x10-13 moles x 100 𝑔


1 𝑚𝑜𝑙𝑒 = 1.77x10-11 g
1.77x10-11 g x 1000 𝑚𝑔 = 1.77x10-8 mg
1𝑔

(b) What is the maximum number of milligrams of AB2 which can dissolve in 200 ml of wash water?

200 ml, Ksp = 10-4


AB2 (s) A+2 (aq) + 2B- (aq)
I 0 0
C +x +2x
E x 2x
Ksp = (x)
(2x)2 10-4 = 4x3
x = 3√10-4 / 4 Ksp = (2(0.029 M)2 (0.029 M)
x = 0.029 M = 4.88x10-5

4.88 𝑥 10 𝑚𝑜𝑙𝑒𝑠
−5 x 0.2 L = 9.76 x10-6 moles
𝐿

9.76 x 10-6 moles x 100 𝑔


1 𝑚𝑜𝑙𝑒 = 9.76x10-4 g
9.76 x 10-4 g x 1000 𝑚𝑔 = 0.976 mg
1𝑔

(c) 3.00 Mm BaB2 is dissolved in 100 ml of water, and 10 per cent in excess of the equivalent amount of
0.10 M A(NO3)2 is added. How many milligrams of AB2 remain unprecipitated?

3.00 Mm BaB2
10 per cent in excess of the equivalent amount of 0.10 M A(NO3)2

BaB2 + A(NO3)2 2AB + Ba (NO3)2


I 0 0
C +2x +x
E 2x x
1 𝑚𝑜𝑙𝑒
3.00 Mm x
1000 𝑀𝑚 = 3 𝑥 10−3 = 0.03 moles
0.1 𝐿
0.10 M x 10 = 1 M
1.03 = 4x3
0.03 + 1M = 1.03 M
x = 3√1.03 / 4
x = 0.63
1.03 = (2x)2 (x)
AB2 = (2(0.63))2
= 1.6 moles/Liter

1.6 moles/Liter x 100 𝑔


1 𝑚𝑜𝑙𝑒 = 160 g x 1000 𝑚𝑔 = 160,000 mg
1𝑔

7. The solid M2N (mol wt. = 75) is soluble to the extent of 0.00015 g per 100 ml.
(a) Find the solubility product for M2N Ans. 32 x 10-

15 M2N = 75 mol wt.

M2N 2M + N
I 0 0
C +2x +x
E 2x x

Ksp = (2x)2 (x)


= [2(2x10-5)2] (2x10-5)
= 32x10-15

(b) Calculate the milligrams of M2N which remain unprecipitated in 300 ml of solution in which the
excess concentration of M+ IS 10-3 M.

300 ml
M+ = 10-3

M2N 2M + N
I 10-3 0
C +2x x
-3
E 10 +2x x

Ksp = [2(10-3+2x)2] (x)


= 1.25x10-6
1.25 𝑥 10−6
𝐿 x 0.3 L = 3.75 x 10-7 moles
3.75 x 10-7 moles x 75 𝑔
1 𝑚𝑜𝑙𝑒 = 2.81 x 10-5 g
1000 𝑚𝑔
2.81 x 10-5 g x
1𝑔 = 0.0281 mg

(c) Calculate the milligrams of M2N which could be lost in 250 ml of wash water.

250 ml

M2N 2M + N
I 0 0
C +2x +x
E 2x x

Ksp = (2x)2 (x)


X = 3√2x10-5 / 4
2x10-5 = 4x3 = 0.017 moles/liter
9.8 𝑥 10−6 𝐿
x 0.25 L = 2.45 x 10-6 moles
2.45 x 10-6 moles x 75 𝑔
1 𝑚𝑜𝑙𝑒 = 1.8 x 10-4 g
1000 𝑚𝑔
1.8 x 10-4 g x
1𝑔 = 0.18 mg

(d) Is the actual loss in washing likely to equal the amount found in (c)?

No. It is due to the fact that by the use of wash water the washings is either greater or lesser in amount
as due to the reason that the underdeveloped precipitate goes along with water. Usually, this type of question is
not considered to have further conduct of calculation as to which it defers the purpose of experimentation. This
is to have experiment as it will help to explore more of the reasons why the actual loss in washing not equal to
the amount found in letter c which is 0.18 mg.

8. The solubility of silver chloride is 10-5 moles per liter. How much wash water may be used in an analysis if
the loss of chloride ion in the wash water is not permitted to exceed 0.1 mg?

moles of 0.1 mg Cl−


Volume = 𝑠𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝑠𝑖𝑙𝑣𝑒𝑟 2.8 𝑥 10−6𝑚𝑜𝑙
𝑐ℎ𝑙𝑜𝑟𝑖𝑑𝑒 = 10 −5 𝑚𝑜𝑙/𝐿 = 0.282 L

9. A sample which weighs 0.5000 g contains 40.00 percent Cl-. The sample is dissolved in 200 ml of water, an
amount of 0.100 M AgNO3 solution is added which is equivalent to the Cl- in the sample and 5.00 ml in excess.
Find the percentage error due to solubility in the precipitating solution. The precipitate is drained free from
supernatant solution and washed with 300 ml 0.05 M HNO3. Find the maximum percentage error due to
solubility in the wash water.
Mass Cl- =.5g*.4= 0.2g=5.63E-3 mol Cl-=mol of AgNO3 w/on the excess=Theoretical AgCl formed
[Cl-] in 200 mL=0.028 M Volume AgNO3 added w/o exess=0.0563L w/excess=0.0613L
Total AgNO3=6.13E-3 mol Total Volume=0.261L

Ksp AgCl =1.7E-10


AgCl Ag+ Cl-
I Solid 0.02348 M 0
C Solid +x +x
E Solid 0.02348 M+x x
-10
Ksp AgCl =1.7E =[0.02348 M+x][x]
[x]=[AgCl]=7.24E-9 M
7.24E − 9 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙
0.261𝐿 ∙ = 1.89𝐸 − 9𝑚 𝑜𝑙 𝐴𝑔𝐶𝑙 → 𝐴𝑚𝑜𝑢𝑛𝑡 𝑙𝑜𝑠𝑡 𝑑𝑢𝑒 𝑡𝑜 𝑠𝑜𝑙𝑢𝑏𝑖𝑙𝑖𝑡𝑦
1000𝑚𝐿 𝑠𝑜𝑙𝑛
AgCl remained due to solubility=5.62999811E-3 mol
1.89𝐸 − 9𝑚𝑜𝑙 𝐴𝑔𝐶𝑙
%𝑒𝑟𝑟𝑜𝑟 = × 100% = 3.356𝐸 − 5%
5.63𝐸 − 3𝑚𝑜𝑙 𝐴𝑔𝐶𝑙

10. What will be the weight of the precipitated AgCl from 0.2000 g of a sample which is 50.00 per cent Cl if
the losses caused by solubility in the precipitating solution and wash water are taken into account? The
conditions of precipitation and washing are:
Final volume of precipitating solution 200 ml
Excess 0.1 M AgNO3 present 1.0 ml
Volume of wash water used 500 ml

Mass of Cl in sample=0.1g=2.8169E-3 mol Cl=molAg=Theoretical mol AgCl formed


In precipitation
Ksp AgCl =1.7E-10
AgCl Ag+ Cl-
I Solid 5E-4 M 0
C Solid +x +x
E Solid 5E-4 M+x x
-4
Ksp AgCl =1.7E-10=[5E M+x][x]

[x]=3.38769E-7M=[AgCl]

Mol AgCl dissolved=6.77538E-8 mol=lost AgCl due to precipitation and common ion effect

AgCl remained=2.816832246E-3 mol


In washing
Ksp AgCl =1.7E-10=[Ag+][Cl-]=[AgCl] 2
[AgCl]=1.3038E-5M
Dissolved AgCl=(1.3038E-5M)(0.5L)=6.5192E-6mol
Final weight of AgCl=2.8103130 mol*143.32g/mol = 0.40277g

11. 0.5000 g AgNO3 and 0.7000 g KBrO3 are added to 250 ml of water. The precipitated AgBrO3 is collected
on a filter and washed with 250 ml of water. After drying in an oven, how much does the precipitated
AgBrO3 weigh?

AgNO3 + KBrO3------------------> AgBrO3 + KNO3


M 1V1= M2V2
M2 = M1V1 / VT
AgNO3= (0.5000)(250ml)
500ml
= 0.25
KBrO3 = (0.7000)(250ml)
500ml
=0.35
AgBrO3 Ag+ +BrO3 –
Ksp = [Ag +][BrO3-] = 7.2 x 10
-3 Q = [Ag +][ BrO3-]
=[0.25][ 0.35]
= 0.0875

12. Find the milligrams of Cl- left in the solution if 50 ml 0.1 M AgNO3 is added to 200 ml of solution which
contains 0.2500 g NaCl. Ans. 3 x 10-4 mg.

AgNO3 + NaCl AgCl + NaNO3

AgNO3 = 0.1 mol AgNO3 X 169.88g = 16.99g


1L 1mol L
NaCl = 0.2500g NaCl x 1 mol x 1 = 0.0214g
1 58.45g .2L L
M 1V1= M2V2
M2 = M1V1 / VT
AgNO3 = (16.99)(50ml) = 3.4 Na = 0.0171 x 23g / 1000mg = 4x10-4
250ml Cl = 0.0171 x 35.45g / 1000 mg = 7x10-4
NaCl = (0.0214)(200ml) = 0.0171 LIMITING /Na – Cl/ = /4x10-4 - 7x10-4/
250ml Cl = 3x10-4

13. 40.00 ml 0.5000 M AgNO3 is added to 230 ml of water which contains 1.942 K2CrO4. What percentage of
chromium remains unprecipitated?
Ans. 0.2%
2AgNO3 + K2CrO4------------------> Ag2CrO4 + 2KNO3
AgNO3 = (0.5)(40ml) = 0.074
1.942 g K2CrO4 x 1 mol/ 118g = 0.016/ .27L
270ml
= 0.061
K2CrO4 = (0.061)(30ml) = 0.052 270ml
Ag2CrO4 = [0.074][ 0.052] Cr =52 x 0.0038
=0.0038 = 0.2
14. M(OH)2 is slightly soluble strong base which dissolves to the extent of 10-6 mole per 100 ml. To 200 ml of
0.1 M MSO4, solid NaOH is added.
(a) How many grams of NaOH have been added before a precipitate begins to form?

M(OH)2
10−6𝑚𝑜𝑙 = 1 x 10-5 M = M2+
S= 100 𝑚𝑙

MSO4 + NaOH(s) M(OH)2 + Na2SO4


0.02 mol 2 x 10-6 mol
4c2 = [OH-]
4 𝑥 10−10 𝑚𝑜𝑙 40 𝑔
4s2 = x 200 ml x = 3.2 x 10-4 g
𝐿 1 𝑚𝑜𝑙

(b) What is the pH when 75 percent of M+2 has precipitated?


Ans. (b) 7.60
Mol MSO4=0.02 mol MSO4=mol M2+

75% mol M2+=0.015mol=mol M(OH)2


∴there is a maximum amount of M(OH)2 dissolved which is 2E-6 mol M(OH)2 in 200 mL or 4E-6 mol OH- in
200 mL soln
[OH-]=2E-5
pH = 7.60

15. The solubility of hydroxide, X(OH)2, is 0.003 g per liter. The molecular weight is 150.
(a) Compute the solubility product

Mol. Wt. = 150 g/mol


OH- = 2(2 x 10-5) = 4 x 10-5 M
OH- = 17g x(OH)2 = x+2 + OH-
+2
x = 133 g = 0.003g/L
0.003𝑔 1 𝑚𝑜𝑙 -5
x = 2 x 10 mol/L Ksp = [x+2] [OH-]2
𝐿 80𝑔

x+2 = 2 x 10-5 M = [2 x 10-5 M] [4 x 10-5 M]


= 8 x 10-10 M
(b) At what pH will a precipitate begin to form if an acid solution of 0.01 M X+2 is neutralized?

[𝑥+2][𝑂𝐻 −]^2 [0.01 𝑀][1.0 𝑥 10−3 𝑀]


K= = = 1.25
c [8 𝑥 10−10 𝑀]
[𝑥(𝑂𝐻2)]
(c) If 1.0 g XSO4 and 1.0 g NH4Cl are added to 100 ml 0.1 M NH3, will a precipitate be obtained? Justify
the answer by a computation of the product [X+2] [OH-]2 and comparison of the value with solubility –product
value.

xCl = XSO4 + NH4Cl NH3 = xSO4 + NH4Cl


[𝑥𝑆𝑂4][𝑁𝐻4𝐶𝑙]
Kc = [𝑥𝐶𝑙] 100 ml 1.0g 1.0g
[10 𝑀] [10 𝑀]
Kc = = 1.0 x 10-14 0.1 M 10 M 10 M
[1.0 𝑥 10 −14 ]

Ksp = [x+2] [Cl-]2


= [1.0 x 10-14] [2.0 x 10-16]
= 2 M xCl
If the solubility-product value is less than the product =
If the solubility-product value is greater than the product = x
Therefore, a precipitate will be obtained

16. At what pH will magnesium hydroxide begin to precipitate from a 0.01 M magnesium sulfate solution?
MgSO4 + 2H = Mg(OH)2 +SO2
M = 0.048g/1L
0.01 MgSO4 = 0.01g/L = 0.048 M Mg(OH)2
Kc = [Mg(OH)2][ SO2]/ MgSO4 pH = -log Mg(OH)2
= 0.01 g MgSO4 x 58.3 g Mg(OH)2 / 1 mol x 1 = -log (0.048M)
mol/120.35g MgSO4 = 1.32
= 0.048g

17. If 25 mg magnesium chloride is added to 100 ml 0.1 N ammonia, will a precipitate be formed?

M1V1=M2V2
M2=(0.03g)(0.1)/1L NH3 + H2O = NH4
M2=0.3 g + OH- (aq)
g = (N)(L)/eq
= (0.1 N)(0.1L)/3
= 0.03 g NH3
Solubility = 0.003g/L x(1 mol/17g) = 1.76 x 10-4 M
Ksp = [1.76 x 10 -4 M][ 1.76 x 10 -4 M]
+
NH4 =1.76 x 10 -4 M
= 3.0976 x 10 -8 M
OH-=1.76 x10 -4 M
18. If 1 g ammonium chloride is added to the solution above, will a precipitate be obtained?

Ksp NH3 = 3.0976 x 10 -8 NH4 = 0.019

M NH4Cl = NH4 + Cl- M Cl- = 0.019


M
1g NH4Cl/1L = 1g/L NH4Cl Ksp = [0.019M][0.019M]
1g/L x 1 mol/50.41g = 0.019 M = 3.61 x 10 -4
NH4Cl
A precipitate will be obtained

20. How many milliliters of 2 M HNO3 must be diluted to 400 ml so that 2.00 g silver acetate will completely
dissolve in this volume?

2g Ag(C2H3O2) x 1mol/166.91g = 333.82 mol


Ag(C2H3O2) M = 333.83 mol/400 mL = 0.8346 M
V1= N2V2/N1
= (0.8346 M)(400mL)/2M
V1= 166.92 mL HNO3
21. 50 ml 0.4 M MgSO4 and 50 ml 1.0 M NaOAc solutions are mixed. Is there any precipitation of Mg(OH)2?

mol=(M)(L)
= (0.04M)(0.05L)
= 0.02 M MgSO4
= (1M)(0.05L)
= 0.05 M NaOAc
CHAPTER 9
1. Consider the effect of the ionization of water, and make a reasonable approximation of the solubility
of cupric hydroxide from its solubility product.

Cu2+ + 2OH → Cu(OH)2(s)


x 2x

Ksp = [ Cu2+] [OH-]2 = 2.2x10-


20
(x)(2x)2 = 2.2x10-20
(x)(4x2) = 2.2x10-20

4x3 2.2x10−20
= 3
√x 3 =
3 x = 1.77x10−7
√5.5x10−21
4 4

2. A solution contains hydrogen, copper, and zinc ions at a concentration of 0.1 M. This solution is
saturated with hydrogen sulfide, to make a final concentration of 0.1 M. Compute the concentration
of copper and zinc ions remaining in solution.

Ksp of CuS = 6.3x10-36

Ksp of ZnS = 2.5x10-22 Cu2+ = 9x10−15M


Ksp of H2S = 1x10- [H+]2 1x10−22
[Zn2+]H2S]
= 1x10−22 = 1
22
[H+]2 [1x10−36]
[Cu+2][H 2S] = [1x10 −22 ]= 1x10−14 [0.3]2
=1
[Zn2+][0.1]
[0.3]2
= 1x10-14
[Cu2+] [0.1]
0.9
Zn2+ = (0.1)(1)
0.09
Cu2+ = (1x10−14)(0.1)
Zn2+ = 9 M

3. Can manganous sulfide, MnS, be quantitatively precipitated by saturating a 0.05 M MnCl2 solution with
H2S?

MnCl2 + H2S → MnS +2HCl


1x10-11 = (0.05M) (x)
MnS → Mn+2 + S- 1x10−11
x= 0.05
Ksp = [Mn2+][S-]
x = 2x10-11
4. Calculate the pH of a buffer solution which will permit all but 0.1 mg of Zn+2 to be precipitated from
200 ml 0.1 M ZnSO4 solution when it is saturated with H2S. How many grams of formic acid and
sodium formate should be added to the solution to prepare this buffer? (Neglect the effects of dilution;
use sufficient sodium formate to have 50 per cent in excess of the amount required to react with the
H+ produced by the precipitation.)

ZnSO4 + H2S → ZnS + H2SO4 1.3x10 mol


pH = 9.25 + log[ −5 ]
1mg 1g 1mol -5 0.02 mol
b= x x = 1.03x10 mol pH = 5.96
1 1000mg 97g

200ml 1L
a= x x 1mol = 0.02 mol formic acid = 46 g/mol
1 1000ml 1L 46𝑔
-10 0.02 mol x = 0.92 g
pka = -log(5.6x10 ) 1𝑚𝑜𝑙
pka = 9.25 Sodium formate = 68 g/mol
pH = pka + log[b] 0.02 mol x 68𝑔 = 1.36 g
a 1𝑚𝑜𝑙

5. How much silver iodide will dissolve if the solid salt is shaken with 250 ml concentrated ammonia
(15 M)? Ans. 1.7 x 10-4 mole

AgI → Ag+ + I- Ksp = 1.5x10-16


Ag + 2NH3 → Ag(NH3)2 Kf = 1.72x107
AgI + 2NH3 → Ag(NH3) +I- K = (Ksp)(Kf)
3.75 0 0
-2x +x +x K = (1.5x10-16)( 1.72x107) = 2.58x10-9
3.75-2x x x

250 ml AgI + 2NH3 → Ag(NH3) +I-


15 M of NH3 [Ag(NH3)] [I−] (x)(x) = x
2 =
= 2
15 mol 0.25 L [NH3]2 (3.75−2x) (3.75−2x)2
x 1 = 3.75
L 2.58x10-9

Cancel 2x, since K is very small


x2
(3.75)2 = 2.58x10-9 x2 = (14.06)( 2.58x10-9)
√x2 = √3.63x10−8
x2
14.06
= 2.58x10-9
x = 1.9x10-4 mole

6. A solution contains the following ions at the stated concentrations:


[Fe+3] = 0.1 M [H+] = 0.1 M [SO4-2] = 0.2 M [Cl-] = 0.1 M
From the point of view of the electrical neutrality of solutions, must any other ions also be presented?
Yes, we need 0.1M +3 ions to maintain electrical neutrality,
The total positive charge is [Fe3+]= 0.1 M [H+]=0.1 M
The total negative charge is [SO4-3]= 0.2 M [Cl-]= 0.1
M
To maintain electrical neutrality, there must be equal number of positive and negative charge. Suppose
[H+] = 0.1 M is neutralized by [Cl--] = 0.1 M then we are left with [Fe3+] = 0.2 M, here if O.1 +3 ions
are neutralized by the 0.1 of [SO4-3], there is still 0.1 of [SO4-3] ions present then we need 0.1 M =3 ions
in the solution.

7. How many equations would have to be set up to determine precisely the pH of a 0.1 M
K2HPO4 solution?

Equations would be established:


a) The dissociation of K2HPO4 is
K2HPO4 2K + HPO 42-
Initial: 0.1 0 0
Final: 0 2(0.1) 0.1
2-
b) Hydrolyzes the anion (HPO4 )
Hpo42- + H2O  PO43- + H3O+
Initial: 0.1 0 0
Change: -x x x
Equilibrium: (0.1)x x x
[𝑃𝑂4][𝐻3𝑂+]
𝐾𝑎 = [𝐻𝑃𝑂4]
-13 (𝑥)(𝑥)
3.6x10 =
(0.1−𝑥) x = 2x10-7 M = [H3O+]
3.6x10-13 = 𝑥^2 ph = - log[H3O+]
(0.1)

Ph = -log [2x10-7] = 6.7

8. Find the pH of a solution made by diluting one drop (0.04 ml) of 0.10 N HCl to 10 liters. Ans. 6.37

N1= 0.1 N V1 = 0.04 Ml V2 = 10 L


N1V1 = N2V2 [H+] = 0.0004 N
(0.1)(0.04) = 0.0004 Ph = -log [H+]
10𝐿
= N 2

After dilution: [HCl] = 0.0004 N HCl -- H+ + Cl-


= -log [0.0004]
= 3.4 pH
9. Repeat problem 8, but use HOAc
0.10 N HOAc = 0.10 M HOAc
Concentration of diluted sample:
1𝑙
(0.04𝑚𝐿)( )(0.10𝑀)
[HOAc] = 1000𝑚𝐿
= 4X10-7 M
10 𝐿

HOAc + H2O  OAc- + H3O+


Initial: 4x10-7-------------- 0--------0
Change: -x ------------------ +x-----+x
Equilibrium: 4x10-7 ----------- x-------x

[𝑂𝐴𝑐−][𝐻3𝑂] [H3O+] = x = 3.9x10-7 m


Ka = [𝐻𝑂𝐴𝑐] Ph= - log [H3O+]
[𝑥][𝑥]
1.8x10-5 = = -log [ 3.9x10-7]
[4𝑥10−7−𝑥]
x = 3.9x10 M -7 = 6.41 pH

10. Find the pH of 0.1 M solutions of:


(a) NaHSO3

NaHSO3----------> Na + HSO3
HSO3 + H2O<===> SO3-2 + H3O
HSO3 + H2O <===> H2SO3 + OH
Ka of HSO3 + H2O <===> SO3-2 + H3O = 1.5x10-2
Ka1= 1.5x10-2 ; pKa1=1.82
Ka2= 1.2x10-7 ;pKa2= 6.32
pH= ½ (pKa1 +
pKa2) pH= ½(1.82 +
6.32) pH= ½(8.14)
pH = 4.07

(b) KHS Ans. (a) 4.63

KHS -- K + HS
HS + H2O<===> H2S +
OH I 0.1 0
0
C –x +x +x
E 0.1-x x x

Kb= Kw/Ka= 1.0x10-14/1.0x10-7


Kb=[ H2S] [OH]/ [ HS]
1.0x10-7=x2/0.1-x
x2= (0.1)( 1.0x10-7)
x= 0.03
pOH= -log(OH)
pOH=
-log(0.03)=1.52
pH=14-pOH=14-
1.52 pH =12.48

11. Compute the degree of hydrolysis for 10-1, 10-3, 10-5, 10-7 M solutions of sodium acetate. Construct a
curve showing ∝ as a function of pC (-log concentration). The degree of hydrolysis is the ratio of
the concentration of acetic acid to the original concentration of salt present.

CH3COONa <===> CH3COO +_ Na


. CH3COO + H2O <===> CH3COOH + OH
0.1x(1-h) 0.1xh 0.1xh
Kh = [CH3COOH] [OH]/ [CH3COO]

10-1 M 10-5 M
Kh= (0.1xh) (0.1xh)/ 0.1(1-h) Kh= (0.00001xh) (0.00001xh)/ 0.00001(1-h)
5.6x10-10 = 0.1xh2 5.6x10-10 = 0.00001xh2
h 2 = 5.6x10-10 /0.1 h 2 = 5.6x10-10 /0.00001
h=7.48x10-5 h=7.48x10-3
OH = (0.1)( 7.48x10-5)= 7.48x10-6 OH = (0.00001)( 7.48x10-3)= 7.48x10-8
H = Kw/OH= 10-14/7.48x10-6=1.34x10-9 H = Kw/OH= 10-14/7.48x10-8=1.34x10-7
pH= -log(H) = -log(1.34x10-9) pH= -log(H) = -log(1.34x10-7)
pH= 8.87 pH= 6.87

10-3 M 10-7 M
Kh= (0.001xh) (0.001xh)/ 0.001(1-h) Kh= (0.0000001xh) (0.0000001xh)/
5.6x10-10 = 0.001xh2 0.0000001(1-h)
h 2 = 5.6x10-10 /0.001 5.6x10-10 = 0.0000001xh2
h=7.48x10-4 h 2 = 5.6x10-10 /0.0000001
OH = (0.001)( 7.48x10-4)= 7.48x10-7 h=0.07
H = Kw/OH= 10-14/7.48x10-7=1.34x10-8 OH = (0.0000001)(0.07)= 7.48x10-9
pH= -log(H) = -log(1.34x10-8) H = Kw/OH= 10-14/7.48x10-9=1.43x10-6
pH= 7.87 pH= -log(H) = -log(1.43x10-6)
pH= 5.84
Degree of Hydrolysis
10
9
8
7
6
5
4
3
2
1
0

0.1 M 0.001 M 0.00001 M 0.0000001 M

12. Make a computation similar to that of problem 8 for the hydrolysis of ammonium chloride, and plot
a curve showing ∝ as a function of pC.

NH4Cl --- NH4 + HCl


NH4 + H2O <===> NH3 +
H3O I 0.10 0 0
C -x +x +x
E 0.10-x x x
Ka = Kw/Kb =1x10-14 / 1.8x10-5 = 5.6x10-10 = [NH3]
[H3O]/[NH4] 5.6x10-10 = x2 / 0.10
x = 7.48x10-6
pH = 5.13

13. Compute the degree of ionization for HOAc at concentrations of 10-1, 10-3, 10-5, 10-7, 10-9 M. Plot ∝
versus –log C.
% ion = X/[HA] x 100
x²= (1.8x10⁻⁵) (0.00001)
1.8x10⁻⁵= [H3O+] [OAc-] / [HOAc]
x = 1.34 x 10⁻⁰⁵
10⁻¹ % ion = (1.34 x 10⁻⁰⁵/0.00001) x 100
1.8 x 10⁻⁵= x²/ 0.1-x % ion = 134%
x²= (1.8 x 10⁻⁵) (0.1) 10⁻⁷
x = 1.34 x 10⁻⁰³ 1.8 x 10⁻⁵= x²/ (1 x 10 ⁻⁷)-x
% ion = (1.34 x 10⁻⁰³/ 0.1) x 100 x²= (1.8 x 10⁻⁵) (1 x 10 ⁻⁷)
% ion = 1.34% x = 1.34 x 10⁻⁰⁶
10⁻³ % ion = (1.34 x 10⁻⁰⁶/ (1 x 10 ⁻⁷)) x 100
1.8x10⁻⁵= x²/ 0.001-x % ion = 1341%
x²= (1.8x10⁻⁵) (0.1) 10⁻⁹
x = 1.34 x 10⁻⁰⁴ 1.8 x 10⁻⁵= x²/ (1 x 10⁻⁹)-
% ion = (1.34 x 10⁻⁰⁴/0.001) x 100 x x²= (1.8 x 10⁻⁵) (1 x
% ion = 13.4% 10⁻⁹) x = 1.34 x 10⁻⁰7
10⁻⁵ % ion = (1.34 x 10⁻⁰³/ (1 x 10⁻⁹)) x 100
1.8 x 10⁻⁵= x²/ 0.00001-x % ion = 13416%
14. Will Fe (OH)3 precipitate from a solution which is 0.1 M in KOH and 0.2 M in K3Fe (CN)6? The
dissociation constant for K3Fe (CN)6 is 10-44.

OH- from NH3+ + H2O


NH3+ + H2O --- NH4+ + OH
I 0.1 0 0
C -x x x
E 0.1-x x x
-5
1.8x10 = 2𝑥

0.1−𝑥
x = √(1.8 𝑥 10−5)(0.1) = 1.34 x 10-3
2

x = [OH-] = 1.34 x 10-3


K3Fe(CN)6 = 10-44

K3Fe(CN)6 +HClO4 = Fe+3 + HCN +


[Fe(CN)6]4- I 0.2 0 0 0
C -x x x x
E 0.2-x x x x
𝑥2
0.2−𝑥= 10-44
x = [Fe ] = 1.26 x 10-15
+3

[Fe+] [OH-]3 = (1.26 x 10-15) (1.34 x 10-3)3


= 2.26 x 10-21
Since ion product value (2.26 x 10-21) exceeds Ksp (10-37), precipitate occurs

15. What concentrations of Fe+3 and Zn+2 ions are in equilibrium with their hydroxides in a buffer solution
made by adding 20 g NaOAc to 150 ml 0.15 M HOAc? Ans. [Fe+3] = 5 x 10-11 M.

NaOAc + H2O <===> HOAc + NaOH


pOH
[OH-] = [NaOH] = Ch = 0.01 x 2.29 x 10-4
= 2.29 x 10-6
pOH = -log [OH] = -log[2.29 x 10-6]
pOH = 5.64
(S) (0.15 + s) = 2.29 x 10-4
0.15𝑠 2.29 𝑥 10−4
0.15 = 0.15
s = 1.5 x 10-3 M
Zn+2 = 1.5 x 10-3 M
Fe+3 = 0.15 + 1.5 x 10-3 = 0.1515 M

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