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By Carl F. Floe, John Chipman

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y.

Jan 4, 1914

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAND,1 NEW YORK, N. Y. BENJAMIN B. THAYER,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,' NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, : NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, . . . NEW YORK, N. Y.

Jan 5, 1915

PRESIDENT BENJAMIN B. THAYER,2 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS; NEW.-YORK, N. Y. TREASURER ' GEORGE C. STONE,1 .NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 8, 1914

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER W. RAYMOND NEW YORK, N. Y.

Jan 5, 1913

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAND,1 NEW YORK, N. Y. BENJAMIN B. THAYER,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ..... ST. Louis, Mo. TREASURER GEORGE C. STONE,' NEW YORK, N. Y. SECRETARY EMERITUS , ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 7, 1915

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y.. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 10, 1914

PRESIDENT CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND NEW YORK, N.Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 1, 1914

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAND,1 NEW YORK, N. Y. BENJAMIN B. THAYER,2 NEW YORK, N.Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,' NEW YORK, N. Y SECRETARY EMERITUS ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 6, 1915

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAND,1 NEW York , N. Y. BENJAMIN B. THAYER,2 . NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,1 NEW YORK, N.Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW York, N. Y.

Jan 4, 1915

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,' NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY. BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 11, 1913

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY. BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 8, 1913

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N: Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORE, N. Y.

Jan 12, 1914

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW. YORK, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,' NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY. BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 7, 1913

PRESIDENT. CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW YORK, N. Y. JAMES F. KEMP, 2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER,1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER. W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, NEW YORK, N. Y.

Jan 12, 1913

PRESIDENT. .CHARLES F. RAND,1 NEW YORK, N. Y. PAST PRESIDENTS. CHARLES KIRCHHOFF,1 NEW York, N. Y. JAMES F. KEMP,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT. BENJAMIN B. THAYER'1 NEW YORK, N. Y. TREASURER. GEORGE C. STONE,' NEW YORK, N. Y. SECRETARY EMERITUS. ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY . BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 6, 1913

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK,. N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 11, 1914

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C: STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 1, 1915

PRESIDENT BENJAMIN B. THAYER,1 NEW YORK, N. Y. PAST' PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F..RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY K. KENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y

Jan 6, 1914

PRESIDENT BENJAMIN B. THAYER,2 NEW YORK, N. Y. PAST PRESIDENTS JAMES F. KEMP,1 NEW YORK, N. Y. CHARLES F. RAND,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 NEW YORK, N. Y. TREASURER GEORGE C. STONE,1 .NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY. BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 7, 1914