PROBLEM SET NO.

3
1. A 0.4 molal aqueous solution of K2SO4 freezes at –1.52°C. Assuming that i is constant with
temperature, calculate the vapor pressure at 25°C and the normal boiling point of the solution.

Solution for vapor pressure:

Given: 𝐵
𝑙𝑜𝑔𝑉𝑃 = 𝐴 −
0.4 molal 𝐶+𝑇
Where:
𝑇𝑓 = −1.52°C
A= 8.07131
B= 1730.630
Solution for normal boiling point: C= 233.426
𝑇𝑓 −𝑇𝑓0 = 𝑖𝑚𝐾𝑓 (1) T = 25°C
𝑉𝑃 = 𝑃𝑤𝑎𝑡𝑒𝑟 = 23.6864
𝑇𝑏 − 𝑇𝑏0 = 𝑖𝑚𝐾𝑏 (2) 1000𝑔 1
𝑃𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 23.6864 𝑚𝑚𝐻𝑔
0.4 𝑚𝑜𝑙 18𝑔
Dividing (1) by (2) 𝑃𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = 𝟑𝟐𝟖𝟗. 𝟕𝟕𝟕𝟖 𝒎𝒎𝑯𝒈
Let x = boiling point of electrolyte solution
1.52 − 0 𝑖𝑚(1.86)
=
𝑥 − 100 𝑖𝑚(0.52)

1.52(0.52)
+ 100 = 𝑥
1.86
𝑥 = 𝟏𝟎𝟎. 𝟒𝟐𝟒𝟗°C
PROBLEM SET NO. 3
2. A solution of HCl, 0.72% by weight, freezes at –0.706◎C. Calculate the apparent molality and the
apparent molecular weight of the HCl.

Given: Solution for molecular weight:

𝑚𝑜𝑙 𝑠𝑜𝑙𝑢𝑡𝑒
𝑇𝑓 = −0.706𝐶 𝑚=
𝑘𝑔 𝑠𝑜𝑙𝑣𝑒𝑛𝑡
0.72
0.72% by wt. HCl 𝑀𝑊
0.3796 =
Solution basis: 100g solution 1 𝑘𝑔
99.28𝑔 1000𝑔
Solution for apparent molality: 𝑔
𝑀𝑊 = 19.1049
𝑚𝑜𝑙
∆𝑇𝑓 = 0 − (−0.706)
∆𝑇𝑓 = 0.706°𝐶
∆𝑇𝑓 = 𝐾𝑓 (𝑚)
0.706℃ = 1.86 𝑚
𝒎𝒐𝒍
𝑚 = 𝟎. 𝟑𝟕𝟗𝟔
𝒌𝒈
PROBLEM SET NO. 3
3. A 2.00 molal HCl solution freezes at –8.86◎C. Calculate the apparent percentage of dissociation
and explain your answer.

2.00 molal HCl

i = 2.38
𝐻𝐶𝑙 → 𝐻 + + 𝐶𝑙 −
v=𝑥+𝑦 =1+1=2

𝑖 = 2.38

𝑖−1
𝛼=
𝑣−1

2.38 − 1
𝛼=
2−1

𝛼 = 2.38
PROBLEM SET NO. 3
5. A solution is 0.5 molar in MgSO4, 0.1 molar in AlCl3, and 0.2 molar in (NH4)2SO4. What is the total
ionic strength?

𝑀𝑔𝑆𝑂4 → 𝑀𝑔2+ + 𝑆𝑂42−

C 0.5 0.5
Z2 4 4
𝐴𝑙𝐶𝑙3 → 𝐴𝑙3+ + 3𝐶𝑙 −
C 0.1 3(0.1)
Z2 9 1
𝑁𝐻4 2𝑆𝑂3 → 𝐴𝑙3+ + 3𝐶𝑙−
C 2(0.2) 0.2 2
Z2 1 4
1 1 1
𝐼 = 2 0.5 4 + 0.5 4 + 2 0.1 9 + 3 0.1 1 + 2 (2.02 + (0.2)(4))
𝐼 = 3.2
PROBLEM SET NO. 3
6. Compare the ionic strengths of 0.1 N solutions of HCl, SrCl2, AlCl3, ZnSO4, and
Fe2(SO4)3.

Given:
0.1 N of HCl, SrCl2, AlCl3, ZnSO4, and Fe2 (SO4)3 C 0.1 2(0.1)
Z2 4 1
C 0.1 0.1 𝐼=
1
0.1 (9) + (3) 0.1 1
2
Z2 1 1 𝐼 = 0.6
1
𝐼= 0.1 + 0.1 1
2
𝐼 = 0.1
C 0.1 0.1
Z2 4 4
C 0.1 3(0.1)
Z2 9 1
1
𝐼= 0.1 (4) + (2) 0.1 1
2
𝐼 = 0.3
PROBLEM SET NO. 3

C 2(0.1) 3(0.1)
Z2 9 4

1
𝐼= (2) 0.1 (9) + (3) 0.1 4
2
𝐼 = 1.5
7. What is the rate of dissipation of energy by the current in the preceding problem in (a) int. watts,
(b) abs. watts, (c) ergs sec–1 , (d) cal sec–1 ?

𝐼 𝑗𝑜𝑢𝑙𝑒 (𝑎𝑏𝑠) 1
a. 189292.543 𝑐𝑎𝑙 𝑥 0.2390 𝑐𝑎𝑙
𝑥 3600 𝑠𝑒𝑐
= 220.0053 𝑤𝑎𝑡𝑡𝑠 𝑖𝑛𝑡.

b.
𝐼 𝑗𝑜𝑢𝑙𝑒 (𝑎𝑏𝑠) 1
189292.543 𝑐𝑎𝑙 𝑥 𝑥 = 220.0053 𝑤𝑎𝑡𝑡𝑠 𝑎𝑏𝑠
0.2390 𝑐𝑎𝑙 3600 𝑠𝑒𝑐
c.
𝐽 1𝑥10−7 𝑒𝑟𝑔𝑠 𝑒𝑟𝑔𝑠
220.0053 𝑥 = 2.2001
𝑠𝑒𝑐 1 𝑗𝑜𝑢𝑙𝑒 𝑠
d.
1 𝑐𝑎𝑙
189292.543 𝑐𝑎𝑙 𝑥 = 52.5813
3600 𝑠𝑒𝑐 𝑠
PROBLEM SET NO. 3
8. When a potential of 110 volts d-c is applied to the terminals of an electric lamp, a
current of 2 amp is found to flow. (a) What is the resistance of the lamp, and (b) how
many calories of heat are dissipated per hour?
𝐸
(a) 𝑅=𝑖
110 𝑣𝑜𝑙𝑡𝑠
𝑅= = 55 𝑜ℎ𝑚𝑠
2 𝑎𝑚𝑝
(b)
3600𝑠𝑒𝑐 2 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1 ℎ𝑟 = 7200 𝐶𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1ℎ𝑟 1𝑠𝑒𝑐𝑜𝑛𝑑
𝑤 = 110 𝑣𝑜𝑙𝑡𝑠 7200 𝐶𝑜𝑢𝑙𝑜𝑚𝑏𝑠 = 792000 𝑣𝑜𝑙𝑡𝑠 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
𝑗𝑜𝑢𝑙𝑒𝑠 1𝑐𝑎𝑙
𝑤 = 792000 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 = 𝟏𝟖𝟗𝟐𝟗𝟐. 𝟓𝟒𝟑 𝒄𝒂𝒍
𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 4.184𝑗𝑜𝑢𝑙𝑒𝑠
PROBLEM SET NO. 3
9. What volume of O2 would be liberated from an aqueous solution of NaOH by a current of 2 A flowing
for 1.5 hours? The temperature is 27◎C and the total pressure is 1 atm.

𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 3600 𝑠𝑒𝑐

2𝑎𝑚𝑝 = 2 1.5ℎ𝑟 = 10800 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
𝑠𝑒𝑐 1 ℎ𝑟
1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 1 𝑚𝑜𝑙𝑒 𝑂2 𝑠𝑒𝑐
10800 𝑐𝑜𝑢𝑙𝑏𝑜𝑚𝑠 = .028 𝑚𝑜𝑙𝑒 𝑂2
96485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 4 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠
𝑎𝑡𝑚 𝐿
0.0278 𝑚𝑜𝑙 (0.08205 )(300.15 𝐿) 1000𝑐𝑐
𝑉= 𝑚𝑜𝑙 𝐾 ( ) = 689.0721 𝑐𝑐
1𝑎𝑡𝑚 1𝐿
PROBLEM SET NO. 3
10. & 11. (a) How long would it take a current of 1 A to reduce completely 80 cc of 0.1 molar Fe2(SO4)3 to FeSO4?
(b) How many cc of 0.1 molar K2Cr2O7 could be reduced to chromic sulfate, Cr2(SO4)3, by the same quantity of
electricity?

(a)
0.1 𝑚𝑜𝑙𝑒 3 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 96485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑖𝑡𝑦 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 80𝑐𝑐 +
1000𝑐𝑐 1𝑚𝑜𝑙𝑒 𝐹𝑒3 1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡
= 2315.64 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1𝑠𝑒𝑐
2315.64 = 𝟐𝟑𝟏𝟓. 𝟔𝟒 𝒔𝒆𝒄
1𝑐𝑜𝑢𝑙𝑜𝑚𝑏

(b)
−
1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 1 𝑚𝑜𝑙𝑒 𝐶𝑟2𝑂72 1000𝑐𝑐
2315.64 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 −
96485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 6 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 0.1 𝑚𝑜𝑙𝑒 𝐶𝑟2𝑂72
= 𝟒𝟎 𝐜𝐜
PROBLEM SET NO. 3
12. What quantity of electricity would be required to reduce 10 g of nitrobenzene, C6H5NO2, completely
to aniline, C6H5NH2? If the potential drop across the cell is 2 volts, how much energy, in calories, is
consumed in the process?

1 𝑚𝑜𝑙𝑒𝐶6𝐻5𝑂2𝑁 6 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 96485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠

10𝑔 𝐶6𝐻5𝑂2𝑁
123 𝑔𝐶6𝐻5𝑂2𝑁 1 𝑚𝑜𝑙𝑒𝐶6𝐻5𝑂2𝑁 1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡
= 𝟒𝟕𝟎𝟔𝟓. 𝟖𝟓𝟑𝟕 𝒄𝒐𝒖𝒍𝒐𝒎𝒃𝒔
𝑊 = 𝐸𝑖𝑡 = 𝐸𝑄
2 𝑗𝑜𝑢𝑙𝑒𝑠
𝑊 = 47065.8537 = 94131.7074
𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1 𝑐𝑎𝑙
92625.6𝑗𝑜𝑢𝑙𝑒𝑠 = 𝟐𝟐𝟏𝟑𝟖 𝒄𝒂𝒍
4.184 𝑗𝑜𝑢𝑙𝑒𝑠
PROBLEM SET NO. 3
13. A AgNO3 solution containing 0.00739 g of AgNO3 per gram of H2O is electrolyzed between silver
electrodes. During the experiment 0.078 g of Ag plate out at the cathode. At the end of the experiment the
anode portion contains 23.14 g of H2O and 0.236 g of AgNO3. What are the transport numbers of Ag+ and
NO3 – ions?

𝑙𝑜𝑠𝑠 𝑖𝑛 𝑐𝑎𝑡𝑖𝑜𝑛 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑎𝑡 𝑎𝑛𝑜𝑑𝑒 𝑑𝑢𝑒 𝑡𝑜 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛

𝑡 +=
𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝑐𝑢𝑟𝑟𝑒𝑛𝑡 𝑝𝑎𝑠𝑠𝑒𝑑
𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝑐𝑢𝑟𝑟𝑒𝑛𝑡𝑠 𝑝𝑎𝑠𝑠𝑒𝑑 :
1 𝑚𝑜𝑙𝑒 𝐴𝑔 1𝑒𝑞𝑢𝑖𝑣𝑒𝑎𝑙𝑒𝑛𝑡 𝐴𝑔
= 0.078𝑔 𝐴𝑔 = 7.231 x 10 − 4
107.8683𝑔 𝐴𝑔 1 𝑚𝑜𝑙𝑒 𝐴𝑔
0.236𝑔 𝐴𝑔𝑁𝑂 1 𝑚𝑜𝑙𝑒 𝐴𝑔𝑁𝑂3 = 1.389 x 10 − 3 moles AgNO3
3
+
169.8683𝑔 𝐴𝑔𝑁𝑂3
𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝐴𝑔 𝑚𝑖𝑔𝑟𝑎𝑡𝑒𝑑
= 7.231 x 10 − 4 + 1.006 x 10 − 3 − 1.389 x 10 − 3 moles AgNO3
= 3.401 x 10 − 4moles AgNO3

3.401 x 10 −4
𝑡 += − = 𝟎. 𝟒𝟕𝟎𝟑
7.231 x 10 4
𝑡 −= 1 − 0.4703 = 𝟎. 𝟓𝟐𝟗𝟕
PROBLEM SET NO. 3
14. The transference numbers of the ions in 1.000 N KCl were determined by the moving boundary method using 0.80
N BaCl2 as the following solution. With a current of 0.0142 A, the time required for the boundary to sweep through a
volume of 0.1205 cc was 1675 sec. What are the transport numbers of K+ and Cl–?

𝑙𝑜𝑠𝑠 𝑖𝑛 𝑐𝑎𝑡𝑖𝑜𝑛 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑎𝑡 𝑎𝑛𝑜𝑑𝑒 𝑑𝑢𝑒 𝑡𝑜 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛

𝑡 +=
𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝑐𝑢𝑟𝑟𝑒𝑛𝑡 𝑝𝑎𝑠𝑠𝑒𝑑
𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
𝑡𝑜𝑡𝑎𝑙 𝑐ℎ𝑎𝑟𝑔𝑒 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟𝑟𝑒𝑑 = 0.0142 1675 𝑠𝑒𝑐𝑜𝑛𝑑𝑠 = 23.785 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
𝑠𝑒𝑐
1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡
23.785 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 = 2.465 x 10 − 4
96485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
0.1205 𝑐𝑐 x 1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡
𝑡 += = 𝟎. 𝟒𝟖𝟖𝟖
1000 𝑐𝑐 2.465 x 10 − 4 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠
𝑡 −= 1 − 𝑡 += 1 − 0.4888 = 𝟎. 𝟓𝟏𝟏𝟐
PROBLEM SET NO. 3
15. A conductivity cell filled with 0.01 demal KCl solution gives at 0C a resistance of 11,210 ohms.
The distance between the electrodes in the cell is 6 cm. Find (a) the cell constant, and (b) the average
cross-sectional area of the electrodes.

(a)
1 1 𝐴 𝐴
𝐿= = = 𝐿𝑠 =
𝑅 𝜌 𝑙 𝑙
1
𝐿𝑠 =
𝜌
𝐾 𝑙
Substituting 𝐿𝑠 = and R = ρ , 𝑤𝑒 𝑔𝑒𝑡
𝑅 𝐴
𝑙 Ls
𝐾= which can then be turned into K =
𝐴 L
Ls 1
K = = 𝐿𝑠 x R = 11210 𝑜ℎ𝑚𝑠 x
L 0.00077362 ohms cm
𝟖. 𝟔𝟕𝟐𝟑
=
𝐜𝐦
l 6𝑐𝑚
A= = = 𝟎. 𝟔𝟗𝟏𝟗 𝒄𝒎𝟐
K
8.6723
𝑐𝑚
PROBLEM SET NO. 3
16. At 25◎C a cell filled with 0.01 demal KCl solution gave a resistance of 484.0 ohms. The
following data for NaCl solutions were taken in the same cell at 25◎C: (a) Calculate ∧ for NaCl
at each concentration, and (b) evaluate ∧O by plotting ∧ against C.5 and
extrapolating to infinite dilution.

Normality 0.0005 0.0010 0.0020 0.0050

1 Resistance 10910 5494 2772 1129

𝐿=
𝑅

0.00140877 0.6819
𝐾 = 𝐿𝑠𝑅 = 484.0 𝑜ℎ𝑚𝑠 x =
ohm cm cm
Solving for L Solving for Ls
1 𝐾 1000𝐿𝑠
𝐿= = 9.1659x10 − 5 𝐿𝑠 = ∧=
10910 𝑅 𝑁
1 − 0.6819 1000 6.2502x10 − 5
𝐿= = 1.8202x 10 4 𝐿𝑠 = = 6.2502x10 − 5 ∧= = 125.004
5494 10910 0.0005
1 −
0.6819 1000 1.2412x10 − 4
𝐿= = 3.6075x10 4 𝐿𝑠 = = 1.2412x10 − 4 ∧= = 124.12
2772 5494 0.001
0.6819 1000 2.451x10 − 4
1 −
𝐿𝑠 = = 2.451x10 − 4 ∧= = 122.55
𝐿= = 8.8574x 10 4 2772 0.002
1129
0.6819 1000 6.0399x10 − 4
𝐿𝑠 = = 6.0399x10 − 4 ∧= = 120.798
1129 0.005
 Sqrt(N) N R L Ls
0.0224 0.0005 10910 9.1659x10-5 6.2502x10-5 125.004
0.0316 0.001 5494 1.8202x10-4 1.241210-4 124.12
0.0447 0.002 2772 3.607510-4 2.45110-4 122.55
0.0707 0.005 1129 8.857410-4 6.039910-4 120.798

1
𝐿=
𝑅
𝐾
𝐿𝑠 =
𝑅

1000𝐿𝑠
∧=
𝑁