Decomposition Potentials of Some Metallic Sulfamates

Author(s): Harold S. Choguill and Francis J. Shell

Source: Transactions of the Kansas Academy of Science (1903-), Vol. 57, No. 3 (Sep., 1954), pp.
386-390
Published by: Kansas Academy of Science
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 Decomposition Potentials of Some Metallic Sulfamates

HAROLD S. CHOGUILL and FRANCIS J. SHELL*

Fort Hays Kansas State College

INTRODUCTION

Sulfamates of nickel, cadmium, copper and other metals have proved

to be satisfactory as electroplating solutions (2),(3). As a result, a study of

the decomposition potentials of the sulfamates of these metals was made.

Sulfamic acid solution and solutions of the sulfamates of copper, nickel,

and cadmium were investigated. A comparison was made of the decom-

position potentials of sulfamates with other salts of the same metals.

METHOD OF INVESTIGATION

Since electrolysis will convert even inert electrodes into active elec-

trodes with back electromotive force (emf), it is necessary to determine

experimentally the minimum voltage required to cause continuous elec-

trolysis of an electrolyte"4). To measure the decomposition voltages, a

series of applied voltage-current readings are taken as current passes

through a solution between two inert electrodes.

Figure 1 shows a characteristic applied voltage-current curve in which

,: .. .

Applied voltage I Applihed Voltoge 2

Fig. Decomposition Potential Curve Fig.2 Decomposition Potential of OIM Sulfamic Acid

Transactions of the Kansas Academy of Science, Vol. 57, No. 3, 1954.

*Present Address: Phillips Petroleum Company, Bartlesville, Oklahoma.

[386]

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 Decomposition Potentials of Metallic Sulfamates 387

AB represents current flow below the decomposition potential and BC

above the potential.

Point B on the curve is considered to be the potential at which steady,

continuous electrolysis occurs and it is often called the static decomposition

potential(1). However, the dynamic decomposition potential or the mini-

mum potential which is necessary to carry on all the changes which take

place during actual electrolysis, at a very slow rate, is more significant.

This value differs considerably from the reversible decomposition poten-

tial which is calculated from free energy data of electrode systems. This

is because other effects of polarization take place than those described

simply by electrode reactions. To find the decomposition potential from

curves such as Figure 1, two methods are used: (1) CD may be extended

to the applied voltage axis, giving a value of E1c1); (2) CB and AB may

be extended until they meet at D, and the projection of that point on the

voltage axis, E2, is regarded as the dynamic potential (5). Certain investi-

gators favor each method of definition.

EXPERIMENTAL

The power source for electrolysis consisted of a variable transformer

and selenium bridge rectifier. The filtered direct current output was passed

through a voltage divider and a continuously variable voltage applied to

two platinum electrodes which were immersed in the solution to be in-

vestigated. Voltage applied to the electrodes was measured with a 20,000

ohm per volt meter and currents with a microammeter or milliammeter as

was needed. The voltmeter used was rated accurate to 1/2 of 1 per cent

while the ammeter was rated accurate to 1 percent. For this reason, read-

ings are not tabulated to exceed two decimal places.

Solutions of sulfamic acid, cadmium sulfamate, copper sulfamate, and

nickel sulfamate were prepared from purified salts. These solutions gave

tests for no foreign ions. Smooth platinum electrodes were used, since

gas bubbles did not cling as readily as to platinized electrodes. Magnetic

stirring was used to agitate the solutions. Applied voltages and the cor-

responding currents were measured at 250C.

DATA AND INTERPRETATIONS

While only the data for 0.1 M solutions of sulfamates is tabulated,

other concentrations of each electrolyte were studied. These solutions

gave somewhat different current-voltage curves, but the decomposition

potentials corresponded closely to those tabulated and illustrated in the

following figures.

Sulfamic Acid

Result of the electrolysis of 0.1 M sulfamic acid at 250C, under the

conditions described above are recorded in Table I.

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 388 The Kansas Academy of Science

Table I. Decomposition Potential Data for 0.1 M Sulfamic Acid

Potential Current Potential Current

(volts) (milliamperes) (volts) (milliamperes)

0.6 0.00 2.1 1.25

1.0 0.00 2.2 2.31

1.4 0.02 2.3 3.75

1.6 0.08 2.4 5.20

1.7 0.12 2.5 7.10

1.8 0.20 2.6 8.75

1.9 0.35 2.7 10.75

2.0 0.65 2.8 13.15

Figure 2 illustrates the plot of applied voltage against current for

the data in Table I in a range that is significant in determining the de-

composition potential. From the graph E, is 1.19 volts and E2 is 1.92

volts.

Cadmium Sulfamate

Result of the electrolysis of 0.1 M cadmium sulfamate solution under

conditions previously specified is shown in Table II.

Table H. Decomposition Potential Data for 0.1 M Cadmium Sulfamate

Potential Current Potential Current

(volts) (milliamperes) (volts) (milliamperes)

0.2 0.02 1.8 0.50

0.4 0.04 2.0 0.80

0.6 0.07 2.2 1.80

0.8 0.09 2.4 4.00

1.0 0.12 2.6 20.10

1.2 0.20 2.8 45.00

1.4 0.30 3.0 72.20

1.6 0.40 3.2 100.40

Figure 3 illustrates the plot of applied voltage-current data in Table

33

II

I Apphed Voltoge 2 01 Appied Vooge

Fig 3 Decomposition Potential of OIM Codmium Sulfamote Fig4 Decomposition Potential of OIM Copper Sulfomote

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 Decomposition Potentials of Metallic Sulfamates 389

II in the critical range of electrolysis. Decomposition potential from this

graph gives E1 to be 2.14 volts and E2 to be 2.16 volts.

Copper Sulfamate

Result of the electrolysis of 0.1 M copper sulfamate solution under

conditions previously specified is shown in Table III.

Table III. Decomposition Potential Data for 0.1 M Copper Sulfamate

Potential Current Potential Current

(volts) (milliamperes) (volts) (milliamperes)

0.2 0.00 1.6 2.15

0.8 0.01 1.7 3.15

1.0 0.02 1.8 4.65

1.1 0.04 1.9 6.20

1.2 0.10 2.0 8.00

1.3 0.35 2.1 10.20

1.4 0.78 2.2 11.21

1.5 1.45 2.3 13.00

Figure 4 illustrates the plot of applied voltage-current data in Table

II in the critical range of electrolysis. Decomposition potential from the

graph indicated E1 to be 1.44 volts and E2 to be 1.45 volts.

Nickel Sulfamate

The result of electrolysis of 0.1 M sulfamate solution under condi-

tions previously specified is shown in Table IV.

Table IV. Decomposition Potential Data for 0.1 M Nickel Sulfamate

Potential Current Potential Current

(volts) (milliamperes) (volts) (milliamperes)

0.2 0.00 2.0 1.30

0.4 0.04 2.2 1.75

0.6 0A12 2.4 2.00

1.0 0.18 2.6 3.30

1.2 0.22 2.8 6.20

1.4 0.52 3.0 10.05

1.6 0.68 3.2 16.00

1.8 1.08 3.4 22.15

Figure 5 illustrates the plot of applied voltage-current data in Table

IV in the critical range of electrolysis. Decomposition potentials from the

graph indicate E1 to be 2.15 volts and E2 to be 2.17 volts.

DISCUSSION OF RESULTS

While it is not possible to make exact comparison with known

potentials from other compounds of the ions investigated since all tables

encountered were compiled under other experimental conditions as to

concentration or temperature, a relatively close correlation does exist.

Sulfamic acid, in concentrations tabulated and in other concentrations in-

vestigated, showed a decomposition potential somewhat above that of

other acids investigated: for example, 1.91 compared to 1.67 for sulfuric

acid(6). No explanation has been suggested.

Metallic sulfamates show closer agreement. Cadmium sulfamate gave

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 390 The Kansas Academy of Science

SI23

Apphied Voltoge 2

Fig 5 Decomposition Potentiol of O.IM Nickel Sulfomate

a potential of 2.15 compared to 2.03 for cadmium sulfate. Copper sulfa-

mate potential was 1.44 compared to 1.49 for copper sulfate and, nickel

sulfamate was 2.16 compared to nickel sulfate at 2.09(6). In all instances

the metal was deposited at the cathode and oxygen released at the anode.

CONCLUSION

Sulfamic acid and the sulfamates of some of the metals show a

normal decomposition on electrolysis, with decomposition potentials well

in accord with that to be predicted from information regarding other com-

pounds of the same positive ion.

LITERATURE CITED

1. CADY, HAMILTON P., Principles of Electrochemistry, Part II Mimeograph

Edition, Lawrence, Kansas. P. 158 (1927).

2. CUPERY, MARTIN E., Ind. and Eng. Chem. 30, 627-630 (1938).

3. GORDON, W. E., and MARTIN E. CUPERY, Ind. and Eng. Chem. 31, 1237-

1238 (1939).

4. PRUTTON, CARL F., and SAMUEL H. MARON, Fundamental Principles of

Physical Chemistry, New York, The Macmillan Company, P. 580

(1951).

5. Ibid., P. 582.

6. Ibid., P. 583.

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