Maron and Frutton Chapter XV.

Transference and Conductance (M&F)

Word Bank
Demal:

Advise: specific conductance of different concentration of KCl solutions (in demal) can be checked
in Maron and Frutton book at page 453.
Problems

1. A potential of 110 volts d-c is applied to the terminals of an electric lamp, and a current of 2 amp
is found to flow through the lamp. (a) What is the resistance of the lamp, and (b) how many calories
of heat are dissipated per hour?
(a) The first step in solving this problem is to remind the Ohms law

𝑖𝑅 = 𝐸
Where E is the potencia, i is the current and R is the resistance. Now, applying the Omhs law we
obtain the value of the resistance R.
𝐸
𝑅=
𝑖
110 𝑣𝑜𝑙𝑡𝑠
𝑅= = 55 𝑜ℎ𝑚𝑠
2 𝑎𝑚𝑝
(b) To solve this problem it is necessary to use the electrical work equation

𝑤 = 𝐸𝑄
Where w is the done electrical work and Q is the transferred charged. The charge is calculated as
follow
3600 𝑠𝑒𝑐 2 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1 ℎ𝑟 × × = 7,200 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1 ℎ𝑟 1 𝑠𝑒𝑐
Now, applying the equation of electrical work we obtain that

𝑤 = 110 𝑣𝑜𝑙𝑡𝑠 × 7200 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 = 792000 𝑣𝑜𝑙𝑡𝑠 × 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠

𝑗𝑜𝑢𝑙𝑒𝑠 1 𝑐𝑎𝑙
𝑤 = 79200 × 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 = 189,300 𝑐𝑎𝑙
𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 4.184 𝑗𝑜𝑢𝑙𝑒𝑠
2. A direct current of 0.5 amp flows through a circuit for 10 min. under an applied potential of 30
int. volts. Find the quantity of electricity transported by the current in (a) int. coulombs, (b) abs.
coulombs, (c) emu and (d) esu.
(a)
𝑖𝑛𝑡. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 60 𝑠𝑒𝑐
0.5 × 10 𝑚𝑖𝑛 × = 300 𝑖𝑛𝑡. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
𝑠𝑒𝑐 1 𝑚𝑖𝑛
(b)
 1 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏
300 𝑖𝑛𝑡. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × = 299.95 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1,000165 𝑖𝑛𝑡.𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
(c)

1 × 10−1 𝑒𝑚𝑢
299.95 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × = 29.995 𝑒𝑚𝑢
1 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏
(d)

2.9978 × 109 𝑒𝑠𝑢

299.95 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × = 8.9919 × 1011 𝑒𝑠𝑢
1 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏

3. What is the rate of the dissipation of the energy by the current mentioned in the preceding
problem in (a) int. watts, (b) abs. watts, (c) erg sec-1 , (d) cal sec -1 ?
(a)

A watt is a work performed at the rate of 1 joule per second, and is obviously a unit of electrical
power.

𝑤 = 𝐸𝑄
If i.t=Q

𝑤 = 𝐸𝑖𝑡
𝑑𝑤 𝐸𝑄
= 𝐸𝑖 = =𝑝
𝑑𝑡 𝑡
30 𝑖𝑛𝑡. 𝑣𝑜𝑙𝑡𝑠 × 300 𝑖𝑛𝑡. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
𝑝(𝑖𝑛𝑡. 𝑤𝑎𝑡𝑡𝑠) = = 2.5 𝑖𝑛𝑡. 𝑤𝑎𝑡𝑡𝑠
3600 𝑠𝑒𝑐
(b)
1 𝑎𝑏𝑠. 𝑤𝑎𝑡𝑡
2.5 𝑖𝑛𝑡. 𝑤𝑎𝑡𝑡𝑠 × = 2.5004 𝑎𝑏𝑠. 𝑤𝑎𝑡𝑡𝑠
0,999835 𝑖𝑛𝑡.𝑤𝑎𝑡𝑡𝑠
(c)
𝑖𝑛𝑡.𝑣𝑜𝑙𝑡𝑠 × 𝑖𝑛𝑡.𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 𝑗𝑜𝑢𝑙𝑒𝑠 × 𝑖𝑛𝑡. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 𝑗𝑜𝑢𝑙𝑒𝑠
2.5 𝑖𝑛𝑡.𝑤𝑎𝑡𝑡𝑠 = 2.5 = 2.5 = 2.5
𝑠𝑒𝑐 𝑖𝑛𝑡. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × 𝑠𝑒𝑐 𝑠𝑒𝑐
𝑗𝑜𝑢𝑙𝑒𝑠 1 × 107 𝑒𝑟𝑔𝑠 𝑒𝑟𝑔𝑠
2.5 × = 2.5 × 107
𝑠𝑒𝑐 1𝑗𝑜𝑢𝑙𝑒 𝑠𝑒𝑐
(d)
𝑗𝑜𝑢𝑙𝑒𝑠 1 𝑐𝑎𝑙 𝑐𝑎𝑙
2.5 × = 0,598
𝑠𝑒𝑐 4.184 𝑗𝑜𝑢𝑙𝑒𝑠 𝑠𝑒𝑐
4. The value of the faraday is 96,485 abs. coulombs per equivalent, while Abogadro’s number is
6.0235 × 1023 . Find the value of the electronic charge in (a) abs. coulombs, (b) int. coulombs, (c)
emu, and (d) esu.
(a)
1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 1 𝑚𝑜𝑙𝑒 𝑒 −
96,486 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × × = 1.6018 × 10−19 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1 𝑚𝑜𝑙𝑒 𝑒 − 6.0235 × 1023 𝑒 −
(b)
1.000165 𝑖𝑛𝑡.𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1.6018 × 10−19 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × = 1.6020 × 10−19 𝑖𝑛𝑡. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏
(c)

1 × 10−1 𝑒𝑚𝑢
1.6018 × 10−19 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × = 1.6018 × 10−20 𝑒𝑚𝑢
1 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏
(d)

2.9978 × 109 𝑒𝑠𝑢

1.6018 × 10−19 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × = 4.8019 × 10−10 𝑒𝑠𝑢
1 𝑎𝑏𝑠. 𝑐𝑜𝑢𝑙𝑜𝑚𝑏

5. A constant direct current flows through an iodine coulometer for a period of 2 hr. At the end of
this time 25.2 cc of 0.08 molar Na 2 S2 O3 are required to react with the liberated I2 . What was the
current passing through the coulometer?

Inside the coulometer occurs the electrochemical reduction of iodide ions into iodine as it is
indicated in the following equation

2𝐼 − → 𝐼2 + 2𝑒 −
The titration of iodine with sodium thiosulfate follows the equation

2𝑁𝑎 2 𝑆2 𝑂3 + 𝐼2 → 𝑁𝑎 2 𝑆4 𝑂6 + 2𝑁𝑎𝐼
As it is known that the titration has consumed 25.2 cc of 0.08 molar Na 2 S2 O3 , we can find the
amount of I2 formed during the electrolysis as follow
0.08 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎 2𝑆2𝑂3 1 𝑚𝑜𝑙𝑒 𝐼2 2 𝑚𝑜𝑙𝑒𝑠 𝐼−
25.2 𝑐𝑐 × × × = 2.016 × 10 −3 𝑚𝑜𝑙𝑒𝑠 𝐼−
1000 𝑐𝑐 2 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎2 𝑆2 𝑂3 1 𝑚𝑜𝑙𝑒 𝐼2
The first equation says that for 2 moles of iodide ions are produced 2 moles of electrons, and
applying the Faraday’s law of the electrolysis we obtain that
2 𝑚𝑜𝑙𝑒𝑠 𝑒 − 96,845 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
2.016 × 10 −3 𝑚𝑜𝑙𝑒𝑠 𝐼− × × = 195.24 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
2 𝑚𝑜𝑙𝑒𝑠 𝐼− 1 𝑚𝑜𝑙𝑒 𝑒 −
As it is known, the current is i=Qt-1
195.24 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 1 ℎ𝑟
× = 0.027 𝑎𝑚𝑝
2 ℎ𝑟 3600 𝑠𝑒𝑐
6. The platinum crucible used in a silver coulometer gains 0.500 g in a certain electrolysis. What
would be the gain in weight of a copper cathode in a cell filled with potassium cuprocyanide
[KCu(CN)2 ] placed in the same circuit.

Firstly, we need to know the amount of charged that have been transferred during the electrolysis
process. These value can be obtained as follow

𝐴𝑔+ + 𝑒 − → 𝐴𝑔

𝐶𝑢+ + 𝑒 − → 𝐶𝑢
1 𝑚𝑜𝑙𝑒 𝐴𝑔 1 𝑚𝑜𝑙𝑒 𝐶𝑢 63.536 𝑔 𝐶𝑢
0.5 𝑔 𝐴𝑔 × × × = 0.29 𝑔 𝐶𝑢
107.8683 𝑔 𝐴𝑔 1 𝑚𝑜𝑙𝑒 𝐴𝑔 1 𝑚𝑜𝑙𝑒 𝐶𝑢
The weight gain by the cathode copper is 0.29 grams.

7. What volume of O2 would be liberated from an aqueous solution of NaOH by a current of 2 amp
flowing for 1 ½ hr? The temperature is 27°C and the total pressure is 1 atm.
The following reaction happens at the anode

4𝑂𝐻 − → 𝑂2 + 2𝐻2 𝑂 + 4𝑒 −
The total charged passed through the circuit can be calculated with the current and the time of the
process
𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 3600 𝑠𝑒𝑐
2 𝑎𝑚𝑝 = 2 × 1.5 ℎ𝑟 = 10,800 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
𝑠𝑒𝑐 1 ℎ𝑟
With the total charged in coulombs it is possible to calculate the amount of moles of O 2 liberated as
follow

1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 1 𝑚𝑜𝑙𝑒 𝑂2
10,800 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × × = 0.02798 𝑚𝑜𝑙𝑒 𝑂2
96,485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 4 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠
Applying the real gas equation PV=nRT we calculate the volume of O 2 liberated
𝑎𝑡𝑚 ∙ 𝐿
0.02798 𝑚𝑜𝑙𝑒𝑠 𝑂2 × 0.082 × 300.15𝐾 1000 𝑐𝑐
𝑉= 𝑚𝑜𝑙 ∙ 𝐾 × = 688.7 𝑐𝑐
1 𝑎𝑡𝑚 1𝐿

8. (a) How long would it take a current of 1 amp to reduce completely 80 cc of 0.1 molar Fe 2 (SO4)3?
(b) How many cc of 0.1 molar Kr2 CrO7 could be reduced to chromic sulfate. Cr2 (SO4)3 . By the same
quantity of electricity?

(a) The problem asks to completely reduce 80 cc of 0.1 molar of Fe 2 (SO4 )3 , it means, to pass the Fe 3+
to Fe(s). The following equation depict the process

𝐹𝑒 3+ + 3𝑒 − → 𝐹𝑒
So, it is needed three electrons per mole of Fe 3+ to be completely reduced. As we know the current
flowing through the circuit is 1 amp (or 1 coulombs per sec), we can determine the time required to
the process to take place knowing the amount of electricity required to completely reduce all the Fe 3+.
The amount of electricity required in the process can be calculated using the Faraday’s law of the
electrolysis.

0.1 𝑚𝑜𝑙𝑒 𝐹𝑒 3+ 3 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 96,485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠

80 𝑐𝑐 × × × = 2,315.64 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1000 𝑐𝑐 1 𝑚𝑜𝑙𝑒 𝐹𝑒 3+ 1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡
Now, we can calculate the time
1 𝑠𝑒𝑐
2,315.64 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × = 2,315.64 𝑠𝑒𝑐
1 𝑐𝑜𝑢𝑙𝑜𝑚𝑏
(b) The process follows the equation below

𝐶𝑟2 𝑂72− + 14𝐻3 𝑂+ + 6𝑒 − → 2𝐶𝑟 3+ + 21𝐻2 𝑂

It can be realized that the Cr passes from the oxidation number 6+ to 3+, so it gains three electrons.
As in the process it is involved to Cr atoms, the total electrons transfer per mole of K 2 Cr2 O7 are six.
Now, applying the Faraday’s law of electrolysis we obtain the volume of 0.1 molar K 2 Cr2 O7 that
reduces the same amount of electricity.

1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 1 𝑚𝑜𝑙𝑒 𝐶𝑟2 𝑂72− 1000 𝑐𝑐

2,315.64 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × × × = 4 𝑐𝑐
96,485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 6 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 0.1 𝑚𝑜𝑙𝑒 𝐶𝑟2 𝑂72−

9. What quantity of electricity would be required to reduce 10 g of nitrobenzene completely to aniline?

If the potential drop across the cell is 2 volts, how much energy, in calories, is consumed in the
process?4
[Reaction in chemsketch]

The electrochemical reduction of nitrobenzene to aniline required the transference of six electrons.
The first step is to identify how much electricity is needed to the process to take place, and then, it is
possible to calculate the electrical work as follow
1 𝑚𝑜𝑙𝑒 𝐶6 𝐻5 𝑂2 𝑁 6 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 96,485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
10 𝑔 𝐶6 𝐻5 𝑂2 𝑁 × × × = 46,312.8 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
123 𝑔 𝐶6 𝐻5 𝑂2 𝑁 1 𝑚𝑜𝑙𝑒 𝐶6 𝐻5 𝑂2 𝑁 1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡

Now, with the following equation the electrical work is calculated

𝑊 = 𝐸𝑖𝑡 = 𝐸𝑄
𝑗𝑜𝑢𝑙𝑒𝑠
𝑊 = 46,312.8 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × 2 = 92,625.6 𝑗𝑜𝑢𝑙𝑒𝑠
𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
1 𝑐𝑎𝑙
92,625.6 𝑗𝑜𝑢𝑙𝑒𝑠 × = 22,138 𝑐𝑎𝑙
4.184 𝑗𝑜𝑢𝑙𝑒𝑠

10. A 4 molal solution of FeCl3 is electrolyzed between platinum electrodes. After the electrolysis the
cathode portion, weighing 30 g, is 3.15 molal in FeCl3 and 1.00 molal in FeCl2 . What are the transport
numbers of Fe 3+ and Cl- ions?
The problem says that the total weight of the solution inside the cathode is 30 g, so we have that
 𝑊 𝐻2 𝑂 + 𝑊 𝐹𝑒𝐶𝑙3 + 𝑊 𝐹𝑒𝐶𝑙3 = 30 𝑔

As it is known, the units molal concentration are moles of solute per Kg of solvent. For 1,000g of
water we have that
3.15 𝑚𝑜𝑙𝑒𝑠 𝐹𝑒𝐶𝑙3 162.204 𝑔 𝐹𝑒𝐶𝑙3
1,000 𝑔 𝐻2 𝑂 × × = 517.24 𝑔 𝐹𝑒𝐶𝑙3
1000 𝑔 𝐻2 𝑂 1 𝑚𝑜𝑙𝑒 𝐹𝑒𝐶𝑙3
1 𝑚𝑜𝑙𝑒 𝐹𝑒𝐶𝑙2 126.751 𝑔 𝐹𝑒𝐶𝑙2
1,000 𝑔 𝐻2 𝑂 × × = 126.751 𝑔 𝐹𝑒𝐶𝑙2
1,000 𝑔 𝐻2 𝑂 1 𝑚𝑜𝑙𝑒 𝐹𝑒𝐶𝑙 2
So

126.751 𝑔 𝐹𝑒𝐶𝑙2 + 517.24 𝑔 𝐹𝑒𝐶𝑙 3 + 1000 𝑔 𝐻2 𝑂 = 1643.991 𝑔

Now, we can obtain the percentage of each compound in the solution and then to determine the
amount of each one in the 30 g that we have in the cathode solution. Percentages: 7.71% of FeCl2 ,
31.46% of FeCl3 and 60.83% of water. In the 30 g of the cathode solution we have 2.313 g FeCl2 ,
9.483 g FeCl3 and 18.249 g of water.
As we supposed that water does not migrate, the amount of water before the electrolysis at the cathode
were 18.249 g. On the other hand, we have that the transference number is given by the current due
to the ion (I- or I+) divided by the total current of the system (I). As I - = z+n+ev- and I+ = z+n+ev+ due
to the condition of electroneutrality (you can follow a detailed explanation in the post of Transference
and Transference numbers), the transference number can be expressed as in the following equation
𝑣+
𝑡+ =
𝑣+ + 𝑣−
Because of the Hittorf’s rule, as it is explained in the post of Determination of Transference numbers,
if the velocities of cations and anions are different, the loss in concentration of ions in the cathode
and anode due to migration is proportional to the speed of each ion. This parallelism between
concentration loss due to migration and the velocity of the ion responsible for it leads to Hittorf’s
rule, which states that
𝐿𝑜𝑠𝑠 𝑖𝑛 𝑐𝑎𝑡𝑖𝑜𝑛 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑎𝑡 𝑎𝑛𝑜𝑑𝑒 𝑑𝑢𝑒 𝑡𝑜 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑣+ 𝑡+
= =
𝐿𝑜𝑠𝑠 𝑖𝑛 𝑎𝑛𝑖𝑜𝑛 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑎𝑡 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 𝑑𝑢𝑒 𝑡𝑜 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛 𝑣− 𝑡−
Glasstone(1942) said that “The total decrease in amount of the electrolyte MA in both compartments
of the experimental cell is equal to the number of equivalents deposited on each electrode; if a
coulometer is included in the circuit, the by the Faraday’s laws the same number of equivalents of
material, no matter what its nature, will be deposited. It follows, therefore, that
(detailed explanation in the post of Determination of Transference numbers)
𝐿𝑜𝑠𝑠 𝑖𝑛 𝑐𝑎𝑡𝑖𝑜𝑛 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑎𝑡 𝑎𝑛𝑜𝑑𝑒 𝑑𝑢𝑒 𝑡𝑜 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛
= 𝑡+
𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝑐𝑢𝑟𝑟𝑒𝑛𝑡 𝑝𝑎𝑠𝑠𝑒𝑑
Amount of cation equivalent lost at anode due to migration is given by the initial amount of FeCl3 at
these compartment and the final amount of the same compound.
The final amount of FeCl3 in grams is 9.351 g as it was determined before, and the initial amount is
 4 𝑚𝑜𝑙𝑒𝑠 𝐹𝑒𝐶𝑙3 162.204 𝑔 𝐹𝑒𝐶𝑙3
18.33 𝑔 𝐻2 𝑂 × × = 11.893 𝑔 𝐹𝑒𝐶𝑙 3
1000 𝑔 𝐻2 𝑂 1 𝑚𝑜𝑙𝑒 𝐹𝑒𝐶𝑙3
The FeCl3 lost at the cathode was 11.893 g – 9.351g = 2.542 g, or 0.0157 moles.
The formation of FeCl2 describe the amount of Fe 3+ lost in the electrolysis process
1 𝑚𝑜𝑙𝑒 𝐹𝑒𝐶𝑙 2
18.33 𝑔 𝐻2 𝑂 × = 0.01833
1000 𝑔 𝐻2 𝑂
So, 2,63 x 10-3 moles of Fe 3+ have arrived at the cathode due to migration or, what is the same, it is
the equivalents lost at the anode due to migration. Now, the transference number is given as follow

2.63 × 10−3 𝑚𝑜𝑙𝑒𝑠 𝐹𝑒 3+ 3 𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠

𝑡+ = × = 0.45
0.01833 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 1 𝑚𝑜𝑙𝑒𝑠 𝐹𝑒 3+
t- = 1 – 0.45 = 0.55
11. A AgNO3 solution containing 0.00739 g of AgNO 3 per gram of H2 O is electrolyzed between silver
electrodes. During the electrolysis 0.078 g of Ag plate out at the cathode. At the end of the experiment
the anode portion contains 23.14 g of H 2 O and 0.236 g of AgNO3 . What are the transport number of
Ag+ and NO3 - ions.
As in the exercise 10., the transport number is calculated with the formula
𝑙𝑜𝑠𝑠 𝑐𝑎𝑡𝑖𝑜𝑛 𝑎𝑡 𝑡ℎ𝑒 𝑎𝑛𝑜𝑑𝑒 𝑑𝑢𝑒 𝑡𝑜 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛
𝑡+ =
𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑜𝑓 𝑐𝑢𝑟𝑟𝑒𝑛𝑡 𝑝𝑎𝑠𝑠𝑒𝑑
The total equivalents of current passed are given by the amount of Ag plated out at the cathode, as
follow
1 𝑚𝑜𝑙𝑒 𝐴𝑔 1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝐴𝑔
0.078 𝑔 𝐴𝑔 × × = 7.231 × 10−4 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠
107.8683 𝑔 𝐴𝑔 1 𝑚𝑜𝑙𝑒 𝐴𝑔
Now, it is necessary to calculate the equivalents of Ag+ lost at the anode due to migration

As it is supposed that water does not migrate from one part of the cell to other, the total amount of
water at the anode during the experiment has been 23.14 g. It is known the concentration of the initial
solution (0.00739g of AgNO3 per g of water), so it is easy to determine the initial amount of salt at
the anode.
0.00739 𝑔 𝐴𝑔𝑁𝑂3
23.14 𝑔 𝐻2 𝑂 × = 0.171 𝑔 𝐴𝑔𝑁𝑂3
1 𝑔 𝐻2 𝑂
The moles of AgNO3 after the electrolysis in the anode compartment is the moles of initial Ag+ ions
plus the Ag+ ions that dissolved from the anode to the solution after the oxidation process, less the
moles of Ag+ that migrated to the cathode.
1 𝑚𝑜𝑙𝑒 𝐴𝑔𝑁𝑂3
0.236 𝑔 𝐴𝑔𝑁𝑂3 × = 1.389 × 10−3 𝑚𝑜𝑙𝑒𝑠 𝐴𝑔𝑁𝑂3
169.8683 𝑔 𝐴𝑔𝑁𝑂3
Equivalents Ag+ migrated (Eq m)
 𝐸𝑞 𝑚 = 7.231 × 10−4 𝑚𝑜𝑙𝑒𝑠 𝐴𝑔𝑁𝑂3 + 1.006 × 10−3 𝑚𝑜𝑙𝑒𝑠 𝐴𝑔𝑁𝑂3 − 1.389
× 10−4 𝑚𝑜𝑙𝑒𝑠 𝐴𝑔𝑁𝑂3 = 3.401 × 10−4 𝑚𝑜𝑙𝑒𝑠 𝑚𝑜𝑙𝑒𝑠 𝐴𝑔𝑁𝑂3 𝑜𝑟 𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠
It is possible now to calculate the transport number of the Ag+ ion and nitrate ions as well
0.0003041
𝑡+ = = 0.47
0.0007231
𝑡− = 1 − 0.47 = 0.53
12. The transference numbers of the ions of 1.000N KCl were determined by the moving boundary
method using a solution 0.80 N BaCl2 as the following solution. Using a current of 0.0142 amp 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- ions.
As it was deduced in the post “Determination of Transference numbers” the transference number of
the cation can be determined by the following equation
𝐿𝑜𝑠𝑠 𝑜𝑓 𝑐𝑎𝑡𝑖𝑜𝑛 𝑎𝑡 𝑡ℎ𝑒 𝑎𝑛𝑜𝑑𝑒 𝑑𝑢𝑒 𝑡𝑜 𝑚𝑖𝑔𝑟𝑎𝑡𝑖𝑜𝑛
𝑡+ =
𝑇𝑜𝑡𝑎𝑙 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑜𝑓 𝑐𝑢𝑟𝑟𝑒𝑛𝑡 𝑝𝑎𝑠𝑠𝑒𝑑
The total equivalents of current passed can be determined using a coulometer in the circuit. If it is
given that the current during the experiment was constant and the value was 0.0142 amp and the
process time was 1675 sec, so, we have that
𝐶𝑜𝑢𝑙𝑜𝑚𝑏𝑠
𝑇𝑜𝑡𝑎𝑙 𝑐ℎ𝑎𝑟𝑔𝑒𝑑 𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟𝑒𝑑 = 0.0142 × 1675 𝑠𝑒𝑐 = 23.785 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
𝑠𝑒𝑐
And applying the Faraday’s law of the electrolysis
1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡
23.785 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 × = 2.465 × 10−4 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠
96,485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠
0.1205 𝑐𝑐 × 1 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡
𝑡+ = = 0.49
1000 𝑐𝑐 × 2.465 × 10−4 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠
𝑡− = 1 − 𝑡+ = 1 − 0.49 = 0.51

13. The cathode, center, and anode chambers of an electrode of an electrolytic cell contain each 10
milliequivalents of HCl in aqueous solution. What will be the number of milliequivalents of HCl in
each compartment after the passage of 5 milliequivalents of electricity through the cell? Assume that
t+ = 0.2 and that H2 is given of at the cathode and Cl2 at the anode.

After the passage of 5 mequivalent of current, there are loss 5 milliequivalents of protons at the
cathode due to the formation of molecular hydrogen and 5 milliquivalents of chloride at the anode.
The process in both cathode and anode are the following, respectively

2𝐻 + + 2𝑒 − → 𝐻2

2𝐶𝑙 − → 𝐶𝑙2 + 2𝑒 −
As each compartment has to preserve the electroneutrality it is necessary a migration of ions. These
migration is given by the transport number of each ion.
Cation
(0.8) x 5 milliquivalents = 4 milliequivalents of H+ migrate
Anion
(0.2) x 5 milliequivalens = 1 milliequivalent of Cl- migrate
In the graph we can follow the process

Each sign (+ and -) represents 1 milliequivalent in the following graph.

Cat ++++++++++ ++++++++++ ++++++++++ Anod
(+) - -- -- -- -- - - -- -- -- -- - - -- -- -- -- - (-)

++++++++++ ++++++++++ +++++

-- -- - - -- -- -- -- - - -- -- -- -- -
++++++ ++++++++++ +++++++++
- -- -- - - -- -- -- -- - - -- -- -- --

At the end of the process the cathode has 6 milliequivalents of HCl, the anode 9 milliequivalents of
HCl and the center chamber 10 milliequivalents of HCl.
14. The conductivity of a cell filled with 0.01 demal (molal) KCl solution gives at 0°C 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.
1 1 𝐴
𝐿(𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑎𝑛𝑐𝑒) = = ( )
𝑅 𝜌 𝑙
R: resistance in omhs
A: electrode area in cm
l: distance between electrodes
1
= 𝐿𝑠
𝜌
ρ: specific resistivity (the resistance of a conductor 1 cm in length and with a cross-sectional area of
1sq cm)
Ls : specific conductance (1 cm cube (not cc) of material, and it is expressed in mh-os)
𝑙
𝐾=
𝐴
𝐿𝑠 𝐾 −1 = 𝐿
𝐿𝑠
𝐾= = 𝐿𝑠 × 𝑅 = 11,210 𝑜𝑚ℎ𝑠 × 0.00077362 𝑜𝑚ℎ −1 𝑐𝑚−1 = 8.672 𝑐𝑚 −1
𝐿
𝑙 6 𝑐𝑚
𝐴= = = 0.692 𝑐𝑚 2
𝐾 8.672 𝑐𝑚−1
Note: the answer in the book says that the area is 1.45 sq cm but these answer is wrong.

15. A conductivity cell filled with 0.10 demal KCl solution gives at 25°C a resistance of 910 omhs.
What will be the resistance when this cell is filled with a solution whose specific conductance at 25°C
is 0.00532 mhos?
The first step is to determine the cell constant K by the same way it was determined in exercise 14 th .

𝐾 = 0.0128560 𝑜𝑚ℎ −1 𝑐𝑚−1 × 910 𝑜𝑚ℎ𝑠 = 11.69896 𝑐𝑚−1

After that, it is determined the resistance of the new solution with the same equation as follow

𝐾 11.69896 𝑐𝑚 −1
=𝑅= = 2203.194 𝑜ℎ𝑚𝑠
𝐿𝑠 0.00531 𝑜𝑚ℎ −1 𝑐𝑚−1
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 then taken in the same cell at 25°C.

Normality Resistance
0.0005 10,910
0.0010 5,494
0.0020 2,772
0.0050 1,128.9

(a) Calculate Λ for NaCl at each concentration, and (b) evaluate Λo by plotting Λ against √𝐶 and
extrapolating to infinite dilution.

Firstly, it is important to know what is equivalent conductance (Λ). The equivalent conductance of
an electrolyte is defined as the conductance of a volume of solution containing one eq uivalent weight
of dissolved substance when place between two parallel electrodes 1 cm apart, and large enough to
contain between them all the solution.
As we know

𝐾 = 𝐿𝑠 𝑅 = 484.0 𝑜ℎ𝑚𝑠 × 0.00140877 𝑜ℎ𝑚−1 𝑐𝑚−1 = 0.682 𝑐𝑚 −1

There are and specific Ls for each concentration. As we have that
𝐾
𝐿𝑠 =
𝑅

N1/2 N R L Ls Λ
0.02236068 0.0005 10,910 9.1659E-05 6.24972E-05 124.994317
0.03162278 0.0010 5,494 0.00018202 0.000124107 124.107026
0.04472136 0.0020 2,772 0.00036075 0.000245975 122.987734
0.07071068 0.0050 1,128.9 0.00088582 0.00060399 120.797945

The graph represents the variation of the equivalent conductance against the squared root of the
concentration in equivalents per liter. (It is possible to download the excel were this table was made,
in the additional information section, doc1).
 Equivalent Conductance
y = -86,233x + 126,87
128
127
126
125
124
Λ 123
122
121
120
-0,01 0 0,01 0,02 0,03 0,04 0,05 0,06 0,07 0,08
sq root (N)

As the equation of the line is y = -86.233x + 126.87, the equivalent conductance at infinite dilution
(Λ0 ) is 126.86 omhs-1 cm2 .
17. At 25°C the equivalent conductances of dilute NaI solutions ar as follow
Molarity Λ
0.0005 125.36
0.0010 124.25
0.0050 121.25
0.0100 119.24
0.0200 116.70
Find Λ0 of NaI at 25°C.

Sq root Nolarity Λ

0.02236068 125.36
0.03162278 124.25
0.07071068 121.25
0.1 119.24
0.14142136 116.70

Equivalent Conductance
128
126 y = -72,016x + 126,63
124
122
Λ

120
118
116
114
-0,02 0 0,02 0,04 0,06 0,08 0,1 0,12 0,14 0,16
Sq root (N)
Λ0 = 126.63 omhs-1 cm2 . The exercise can be downloaded in an excel document (Doc1 – Additional
information).

18. From the following equivalent conductances at infinite dilution at 18°C, find Λ 0 for NH4 OH at
18°C.
Compound Λ0
Ba(OH)2 228.8
BaCl2 120.3
NH4 Cl 129.8

Page 456 M&F. Kohlrausch’s law of independent migration of ions: this law states that at infinite
dilution, where dissociation for all electrolytes is complete and where all interionic affects disappear,
each ion can be considered to migrate independently of its co-ions, and thus to contribute its definite
share to the total equivalent conductance of the electrolyte. Further, if this be the case, the
conductance due to a particular ion at infinite dilution should depend only on the nature of the ion,
and not at all on the co-ion with which it is associated. In other words, the law of independent
migration of ions states that Λ0 of any electrolyte is the sum of the equivalent condutances of the ions
composing it, provided, of course, that the solvent and temperature are the same.

Λ0 = 𝑙 0+ + 𝑙 0−
Λ0 𝑁𝐻4 𝑂𝐻 = Λ0 𝑁𝐻4 𝐶𝑙 − Λ0 𝐵𝑎𝐶𝑙 2 + Λ0 𝐵𝑎(𝑂𝐻 )2
1 1
Λ0 𝑁𝐻4 𝑂𝐻 = 𝑙 0+𝑁𝐻4+ − 𝑙 0+𝐵𝑎2+ + 𝑙+0 𝐵𝑎 2+ + 𝑙 0−𝐶𝑙− − 𝑙−0 𝐶𝑙− + 𝑙 0−𝑂𝐻−
2 2
Λ0 𝑁𝐻4 𝑂𝐻 = 𝑙+0 𝑁𝐻4+ + 𝑙 0−𝑂𝐻−
Λ0 𝑁𝐻4 𝑂𝐻 = 129.8 − 120.3 + 228.8 = 238.8

19. At 25°C the equivalent conductance of a 0.02 molar AgNO 3 solution is 128.7, while the transport
number of Ag+ is 0.477. Calculate the equivalent ionic conductance and the ionic mobilities of Ag+
and NO3 - in a 0.02 molar solution of AgNO 3 .

Λ AgNO3 = 𝑙+ 𝐴𝑔+ + 𝑙 −𝑁𝑂3−

Λ AgNO3 = 𝑡+ Λ AgNO3 + 𝑡− Λ AgNO3
𝑙+ 𝐴𝑔+ = 0.477 × 128,7 = 61,3899
𝑙 −𝑁𝑂3− = 0.523 × 128.7 = 67.3101

20. In measuring the mobility of H+ ions by the moving boundary procedure, it I observed that the
boundary moves a distance of 4 cm in 12.52 min. The voltage drop across the cell before the formation
of the boundary is 16 volts. The distance between electrodes is 9.6 cm. Calculate from these data the
mobility and ionic conductance of hydrogen ions.
If the potential drop before the formation of the boundary is 16 volts and the distance between the
electrodes is 9.6 cm, the voltage drop per centimeter (V) is
16 𝑣𝑜𝑙𝑡𝑠
𝑉= = 1.666 𝑣𝑜𝑙𝑡𝑠 𝑐𝑚−1
9.6 𝑐𝑚
Supposing that the protons only moved in the y-axe of the plane (a linear movement), the drift velocity
of the ions is given by

4 𝑐𝑚 1 𝑚𝑖𝑛 𝑐𝑚
𝑢+ = × = 5.3248 × 10−3
12.52 𝑚𝑖𝑛 60 𝑠𝑒𝑐 𝑠

As the mobility depends of the potential drop, the formula to determine it is the following

−3 𝑐𝑚
𝑢+ 5.3248 × 10 𝑠𝑒𝑐 𝑐𝑚 2
𝑣+ = = = 0.0032
𝑉 1.666 𝑣𝑜𝑙𝑡𝑠 𝑐𝑚−1 𝑣𝑜𝑙𝑡𝑠 𝑠𝑒𝑐
21. At 18°C the mobility at infinite dilution of the ammonium ion is 0.00066 cm / second, while that
of the chlorate ion is 0.00057 cm / second. Calculate Λ0 of ammonium chlorate and the transport
numbers of the two ions.

As it is deduced in the post “Absolute velocity of ions (or mobility)” the mobility can be expressed
in terms of equivalent ionic conductance

𝑙+
𝑣+ =
∝𝐹
𝑙−
𝑣− =
∝𝐹

The ammonium chloride is a strong electrolyte so in aqueous solution at infinite dilution it is

completely dissociated. In this particular case α = 1. On the other hand, it is known that

Λ = 𝑙 + + 𝑙 − = 𝑡 + Λ + 𝑡− Λ

So

𝑣+ 𝐹
= 𝑡+
Λ
𝑣− 𝐹
= 𝑡−
Λ

From those equations it is possible to calculate the value of the equivalent conductance at infinite
dilution of the salt and the transport number of each ion.

𝑐𝑚 2 𝑐𝑚2
Λ0 𝑁𝐻4(𝑇=18°𝐶) = 𝐹 (𝑣+ + 𝑣− ) = 96,485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 (0.00066 + 0.00057 )
𝑣𝑜𝑙𝑡𝑠 𝑠𝑒𝑐 𝑣𝑜𝑙𝑡𝑠 𝑠𝑒𝑐
𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 𝑐𝑚2
= 118.67
𝑣𝑜𝑙𝑡𝑠 𝑠𝑒𝑐
The transport numbers can be calculated as follow

0.00066 𝑐𝑚 2 𝑣𝑜𝑙𝑡𝑠−1 𝑠𝑒𝑐1 × 96485 𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠

𝑡+ = = 0.537
𝑐𝑜𝑢𝑙𝑜𝑚𝑏𝑠 𝑐𝑚 2
118.67
𝑣𝑜𝑙𝑡𝑠 𝑠𝑒𝑐

𝑡− = 1 − 𝑡+ = 0.463

22. For AgNO3 in aqueous solution Λ0 = 133.36 at 25°C. Using the Onsager equation find Λ for a
0.0010 molar solution at the same temperature, and compare the result with the experimentally
observed value of Λ = 130.52

(See the post “Interionic Attraction Theory of Conductance” for more details). For the special case of
1-1 electrolytes in water at 25°C, for which z+ = 1 and z- = 1, D = 78.55, and η = 0.008949 poise, the
equation of Onsager is reduced to the following expression

Λ = Λ0 − [θΛ0 + 𝜎]√𝐶

θ = 0.2273 and σ = 59.78

Λ = 133.36 − [0.2273 × 133.36 + 59.78]√0.0010 = 130.51

23. At 25°C the resistance of a cell filled with 0.01 demal of KCl is 525 ohms. The resistance of the
same cell filled with 0.1N NH 4 OH is 2030 ohms. What is the degree of dissociation of NH 4 OH in this
solution?

NH4OH is a weak electrolyte so

Λ
∝=
Λ𝑒

Ls KCl 0.01N at 25°C = 0.00140877

𝐾 = 𝐿𝑠 𝑅 = 0.00140877 × 525 = 0.7396 𝑐𝑚 −1

Λ𝑒 = 𝑙 0+ + 𝑙 0− = 73.4 + 198 = 272.3

0.7396 𝑐𝑚−1
𝐿𝑠 (𝑁𝐻4 𝑂𝐻 0.1𝑁) = = 3.643 × 10−4
2030 𝑜𝑚ℎ𝑠

1000𝐿𝑠 1000 × 3.643 × 10−4

Λ = 𝐿𝑠 𝑉𝑒 = = = 3.643
𝐶 0.1
Λ 3.643
∝= = = 0.0134
Λ𝑒 272.3
24. What will be the resistance of the cell used in the preceding problem when it is filled with H2O
having a specific conductance of 2 x 10-6 mho?

0.7396 𝑐𝑚 −1
𝑅= = 369,800
2 × 10−6 𝑚ℎ𝑜

25. The specific conductance at 25°C of a saturated aqueous solution of SrSO 4 is 1.482 x 10-4 mho,
while that of the H2 O used is 1.5 x 10-6 mho. Using the data in Table 6, determine at 25°C the solubility
in grams per liter of SrSO 4 in water.

𝐿𝑠(𝑠𝑎𝑙𝑡) = 𝐿𝑠 − 𝐿𝑠(𝐻2𝑂)

𝐿𝑠(𝑠𝑎𝑙𝑡) = (1.482 × 10 −4 − 1.4 × 10−6 ) 𝑚ℎ𝑜 = 1.467 × 10−4 𝑚ℎ𝑜

The equivalent conductance of the salt is

1 1
Λ0 = 𝑙 0+𝑆𝑟2+ + 𝑙 0−𝑆𝑂42− = 58.46 + 79.8 = 138.26
2 2

Since the solution is very dilute (because of the difficult solubility of the salt), the equation to
determine the concentration is

1000𝐿𝑠 1000 × 1.467 × 10−4 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 183,68 𝑔𝑟𝑎𝑚𝑠 𝑆𝑟𝑆𝑂4

𝐶= = = 1.061 × 10 −3 ×
Λ0 138.26 𝐿 2 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠
= 0.097 𝑔𝑟𝑎𝑚𝑠 𝑙𝑖𝑡𝑒𝑟 −1

26. In the titration of 25.0 cc (diluted to 300 cc) of NaC 2 H3 O2 solution with 0.0972 N HCl solution
the following data were found:

Volume of HCl Used Conductace X 104

10.0 3.32
15.0 3.38
20.0 3.46
45.0 4.64
50.0 5.85
55.0 7.10

What is the strength of the Na 2 H3 O2 solution in moles per liter?

To determine the strength of these salt, the first step is to plot the volume of HCl used during the
titration against the conductance
 +

Once the graph is done, the next step is to get the linear equation of the data before and after the final
point of the titration. As the intercept point of the two lines is the final point, the next step is to match
both equations and to find the x (volume of HCl used) to achieve the final point, as follow

140𝑥 + 31767 = 2460𝑥 − 64367

31767 + 64367 = 2460𝑥 − 140𝑥

96134 = 2320𝑥

96134
𝑥= = 41.44
2320

41.44 cc is the volume of HCl 0.0972 N required to neutralize the solution of sodium acetate. With
this information it is possible to calculate the strength of the sodium acetate before de dilution.
0.0972 𝑚𝑜𝑙𝑒𝑠 𝐻𝐶𝑙 1 𝑚𝑜𝑙𝑒 𝑁𝑎𝐶2 𝐻3 𝑂2
41.44 𝑐𝑐 𝐻𝐶𝑙 × × = 4.028 × 10−3 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎𝐶2 𝐻3 𝑂2
1000 𝑐𝑐 1 𝑚𝑜𝑙𝑒 𝐻𝐶𝑙
4.028 × 10−3 𝑚𝑜𝑙𝑒𝑠 𝑁𝑎𝐶2 𝐻3 𝑂2 1000 𝑐𝑐
× = 0.16 𝑀
25 𝑐𝑐 1 𝑙𝑖𝑡𝑒𝑟
0.16 𝑀 × 12 + 0.16 𝑀 × (−1) 2
𝐼= = 0. 16 𝑀
2